KR101380065B1 - Photocurable resin composition - Google Patents
Photocurable resin composition Download PDFInfo
- Publication number
- KR101380065B1 KR101380065B1 KR1020127000783A KR20127000783A KR101380065B1 KR 101380065 B1 KR101380065 B1 KR 101380065B1 KR 1020127000783 A KR1020127000783 A KR 1020127000783A KR 20127000783 A KR20127000783 A KR 20127000783A KR 101380065 B1 KR101380065 B1 KR 101380065B1
- Authority
- KR
- South Korea
- Prior art keywords
- group
- resin composition
- carbon atoms
- photocurable resin
- groups
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 60
- 229920005989 resin Polymers 0.000 claims abstract description 91
- 239000011347 resin Substances 0.000 claims abstract description 91
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 239000003999 initiator Substances 0.000 claims abstract description 9
- -1 vinylene, phenylene, biphenylene Chemical group 0.000 claims description 128
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 229920001187 thermosetting polymer Polymers 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 125000003277 amino group Chemical group 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 125000003282 alkyl amino group Chemical group 0.000 claims description 12
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000004957 naphthylene group Chemical group 0.000 claims description 4
- 125000005556 thienylene group Chemical group 0.000 claims description 4
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 3
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 3
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000005551 pyridylene group Chemical group 0.000 claims description 3
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000016 photochemical curing Methods 0.000 claims description 2
- 229910000679 solder Inorganic materials 0.000 abstract description 11
- 239000000049 pigment Substances 0.000 description 93
- 239000010408 film Substances 0.000 description 60
- 239000003822 epoxy resin Substances 0.000 description 44
- 229920000647 polyepoxide Polymers 0.000 description 44
- 239000000203 mixture Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 34
- 239000010949 copper Substances 0.000 description 29
- 229910052802 copper Inorganic materials 0.000 description 29
- 238000005476 soldering Methods 0.000 description 23
- 239000000126 substance Substances 0.000 description 23
- 239000000758 substrate Substances 0.000 description 22
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- 238000013329 compounding Methods 0.000 description 18
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 18
- 239000004593 Epoxy Substances 0.000 description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 17
- 239000005056 polyisocyanate Substances 0.000 description 16
- 229920001228 polyisocyanate Polymers 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002981 blocking agent Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 11
- 239000012948 isocyanate Substances 0.000 description 11
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- 229910052753 mercury Inorganic materials 0.000 description 11
- 229920003319 Araldite® Polymers 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000003086 colorant Substances 0.000 description 10
- 238000011109 contamination Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013039 cover film Substances 0.000 description 8
- 239000000806 elastomer Substances 0.000 description 8
- 229920003986 novolac Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical group S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000004056 anthraquinones Chemical class 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 230000006870 function Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 6
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 5
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 5
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 229930003836 cresol Natural products 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 150000003553 thiiranes Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 4
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 4
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000004292 cyclic ethers Chemical class 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 4
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 description 4
- 229960001545 hydrotalcite Drugs 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 230000011987 methylation Effects 0.000 description 4
- 238000007069 methylation reaction Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229960003742 phenol Drugs 0.000 description 4
- 229950000688 phenothiazine Drugs 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 150000004294 cyclic thioethers Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000003566 oxetanyl group Chemical group 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
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Abstract
본 발명은 광경화성 수지 조성물에 있어서, 분자 내에 2개의 옥심에스테르기를 갖는 광중합 개시제, 카르복실기 함유 수지, 분자 중에 2개 이상의 에틸렌성 불포화기를 갖는 화합물을 포함함으로써 고감도이고, 건조 도막의 지촉 건조성이 우수하고, 경화 시 등의 아웃 가스의 발생을 억제함과 동시에, 예를 들면 인쇄 배선판의 솔더 레지스트를 형성할 때에, 우수한 위치 정렬 정밀도와 높은 생산성, 신뢰성을 겸비하는 것이 가능해진다.The photocurable resin composition is highly sensitive by including a photopolymerization initiator having two oxime ester groups in a molecule, a carboxyl group-containing resin, and a compound having two or more ethylenically unsaturated groups in the molecule, and excellent in the dryness of the dry coating film. In addition, it is possible to suppress generation of outgases during curing and to combine excellent positioning accuracy, high productivity, and reliability, for example, when forming a solder resist of a printed wiring board.
Description
본 발명은 예를 들면 프린트배선 기판의 솔더 레지스트 등으로서 이용되는 광경화성 수지 조성물에 관한 것이다.TECHNICAL FIELD This invention relates to the photocurable resin composition used, for example as a soldering resist of a printed wiring board.
종래, 인쇄 배선판용 솔더 레지스트를 패터닝할 때, 포토마스크를 접촉시키는 접촉 노광 방식이 주류였다. 그러나, 최근에 인쇄 기판의 고밀도화 등에 따라, 우수한 위치 정렬 정밀도의 관점에서, 포토마스크를 이용하지 않는 다이렉트(직묘) 노광이나 분할 투영 노광이 보급되고 있다.Conventionally, when patterning the soldering resist for printed wiring boards, the contact exposure system which makes a photomask contact is mainstream. However, in recent years, with high density of printed circuit boards, direct (straight drawing) exposure and split projection exposure that do not use a photomask have become widespread in view of excellent positioning accuracy.
다이렉트 노광은 레이저광 등에 의해 직접 주사하면서 노광하는 것으로서, 분할 투영 노광은 투영형 노광기를 이용하여, 작은 노광 면적에서 위치 정렬을 행하면서 노광을 반복하는 것이다. 이와 같이, 패턴 형성된 배선판 상의 솔더 레지스트층을 주사 또는 반복하여 노광하기 때문에, 적정 노광량이 200 mJ/㎠ 이상인 종래의 솔더 레지스트로는 노광에 매우 시간이 걸린다는 문제가 있다.Direct exposure is exposure while scanning directly with a laser beam or the like, and divisional projection exposure is to repeat exposure while aligning in a small exposure area using a projection exposure machine. Thus, since the soldering resist layer on a patterned wiring board is exposed or scanned repeatedly, there exists a problem that exposure takes very time with the conventional soldering resist whose appropriate exposure amount is 200 mJ / cm <2> or more.
따라서, 높은 광중합 능력을 발휘할 수 있는 솔더 레지스트 조성물이 제안되어 있다. 예를 들면, 특허문헌 1에 있어서는, 글리시딜메타크릴레이트와 메틸메타크릴레이트의 공중합물 등의 에폭시기 함유 중합체에 아크릴산을 부가하고, 또한 산무수물을 부가시키고, 생성된 카르복실기에 4-히드록시부틸글리시딜아크릴레이트를 반응시킨 포토레지스트 잉크가 예시되어 있다. 그러나, 주쇄에 대하여 측쇄의 분자가 매우 길고, 또한 분지하고 있기 때문에, 건조 도막의 지촉 건조성이 매우 나쁘다는 문제가 있다.Therefore, the soldering resist composition which can exhibit high photopolymerization capability is proposed. For example, in Patent Literature 1, acrylic acid is added to an epoxy group-containing polymer such as a copolymer of glycidyl methacrylate and methyl methacrylate, an acid anhydride is added, and 4-hydroxy is produced in the carboxyl group. Examples of photoresist inks in which butylglycidyl acrylate is reacted are illustrated. However, since the molecules of the side chain are very long and branched with respect to the main chain, there is a problem that the touch drying property of the dry coating film is very bad.
또한, 특허문헌 2, 3에 있어서는, 광중합 개시제로서 옥심에스테르 개시제를 사용한 솔더 레지스트 조성물이 개시되어 있다. 이러한 솔더 레지스트 조성물에 따르면 양호한 지촉 건조성을 얻을 수 있다. 그러나, 다이렉트 노광 등의 노광 방식에 있어서는, 조성물의 감도가 생산성에 크게 영향을 주는 것으로부터, 한층더 초고감도화가 요구되고 있다. 또한, 광중합 개시제의 성분이 아웃 가스로서 휘발함으로써 오염이 생긴다는 문제가 있다.Moreover, in patent document 2, 3, the soldering resist composition which used the oxime ester initiator as a photoinitiator is disclosed. According to such a soldering resist composition, favorable touch drying property can be obtained. However, in exposure systems, such as direct exposure, super high sensitivity is calculated | required further because the sensitivity of a composition has a big influence on productivity. Moreover, there exists a problem that contamination arises by volatilizing the component of a photoinitiator as outgas.
예를 들면, 포토마스크를 솔더 레지스트층에 접촉시키지 않는 다이렉트 노광이나 분할 투영 노광에 있어서는, 노광 시에 광중합 개시제의 성분이 아웃 가스로서 휘발하여, 노광 장치 내의 광학 부품이 오염될 가능성이 있다. 또한, 양호한 땜납 내열성을 부여하기 위해서, 통상 솔더 레지스트층의 현상 후, 열경화 또는 UV 노광으로 후경화를 행하고, 또한 후속 공정에서 리플로우에 의해 실장이 행해진다. 그 때에, 광중합 개시제의 성분이 아웃 가스로서 휘발하고, 냉각되어 고화하고, 그것이 작업 환경의 오염의 원인이 된다.For example, in the direct exposure or the split projection exposure in which the photomask is not in contact with the solder resist layer, the component of the photopolymerization initiator may volatilize as the outgas during exposure, resulting in contamination of the optical component in the exposure apparatus. In addition, in order to impart good solder heat resistance, after curing of the solder resist layer, post-curing is usually performed by thermosetting or UV exposure, and mounting is performed by reflow in a subsequent step. In that case, the component of a photoinitiator volatilizes as outgas, it is cooled, it solidifies, and it becomes a cause of contamination of a working environment.
따라서, 아웃 가스를 억제하기 위한 수법이 여러가지 검토되고 있다(예를 들면 특허문헌 4 등 참조). 그러나, 인쇄 기판의 고밀도화, 고성능화 등에 따라, 보다 오염을 억제할 것이 요구되고 있고, 한층더 아웃 가스 발생의 억제가 필요하다.Therefore, various methods for suppressing outgas are examined (for example, refer patent document 4). However, with higher density, higher performance, and the like of printed boards, it is required to further suppress contamination, and further suppression of outgas generation is required.
본 발명은 고감도이고, 건조 도막의 지촉 건조성이 우수하고, 경화 시 등의 아웃 가스의 발생을 억제함과 동시에, 예를 들면 인쇄 배선판의 솔더 레지스트를 형성할 때에, 우수한 위치 정렬 정밀도와 높은 생산성, 신뢰성을 겸비하는 것이 가능한 광경화성 수지 조성물을 제공하는 것을 목적으로 한다.The present invention is highly sensitive, excellent in the dryness of the dry coating film, while suppressing the outgas generation during curing, for example, when forming a solder resist of a printed wiring board, excellent alignment accuracy and high productivity. And an object of the present invention is to provide a photocurable resin composition capable of having reliability.
본 발명의 일 양태에 따르면, 분자 내에 2개의 옥심에스테르기를 갖는 광중합 개시제, 카르복실기 함유 수지, 분자 중에 2개 이상의 에틸렌성 불포화기를 갖는 화합물을 포함하는 것을 특징으로 하는 광경화성 수지 조성물이 제공된다.According to one aspect of the present invention, there is provided a photocurable resin composition comprising a photopolymerization initiator having two oxime ester groups in a molecule, a carboxyl group-containing resin, and a compound having two or more ethylenically unsaturated groups in the molecule.
이러한 구성에 의해, 고감도이고, 건조 도막의 지촉 건조성이 우수하고, 경화 시 등의 아웃 가스의 발생을 억제함과 동시에, 인쇄 배선판의 솔더 레지스트를 형성할 때에, 오염을 억제하여, 우수한 위치 정렬 정밀도와 높은 생산성, 신뢰성을 겸비하는 것이 가능해진다.By this structure, it is highly sensitive, excellent in the touch-drying property of a dry coating film, suppresses generation | occurrence | production of the outgas at the time of hardening, and suppresses contamination when forming the soldering resist of a printed wiring board, and excellent position alignment. It is possible to combine precision, high productivity and reliability.
또한, 본 발명의 일 양태의 광경화성 수지 조성물에 있어서, 광중합 개시제는 카르바졸 구조를 갖는 것이 바람직하다. 카르바졸 구조를 갖는 것에 의해, 광 조사에 의해 옥심에스테르기에 있어서 라디칼이 발생(광해열)되고 남은 카르바졸 2량체의 분자량이 커서, 휘발이 감소되기 때문에, 아웃 가스의 발생을 억제하는 것이 가능해진다.Moreover, in the photocurable resin composition of 1 aspect of this invention, it is preferable that a photoinitiator has a carbazole structure. By having a carbazole structure, radicals are generated (photothermal heat) in the oxime ester group by light irradiation, and the molecular weight of the remaining carbazole dimer is large and volatilization is reduced, so that generation of outgas can be suppressed. .
또한, 본 발명의 일 양태의 광경화성 수지 조성물에 있어서, 광중합 개시제는 하기 화학식 I로 표시되는 옥심에스테르 화합물인 것이 바람직하다. 이러한 옥심에스테르 화합물을 이용함으로써 보다 휘발이 감소되어, 아웃 가스에 의한 오염을 억제하는 것이 가능해진다.Moreover, in the photocurable resin composition of 1 aspect of this invention, it is preferable that a photoinitiator is an oxime ester compound represented by following General formula (I). By using such an oxime ester compound, volatilization is reduced more and it becomes possible to suppress the contamination by outgas.
<화학식 I>(I)
(식 중, R1은 수소 원자, 탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 페닐기, 페닐기(탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 아미노기, 탄소수 1 내지 8의 알킬기를 갖는 알킬아미노기 또는 디알킬아미노기에 의해 치환되어 있음), 나프틸기(탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 아미노기, 탄소수 1 내지 8의 알킬기를 갖는 알킬아미노기 또는 디알킬아미노기에 의해 치환되어 있음)를 나타내고, R2, R3은 각각 수소 원자, 탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 할로겐기, 페닐기, 페닐기(탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 아미노기, 탄소수 1 내지 8의 알킬기를 갖는 알킬아미노기 또는 디알킬아미노기에 의해 치환되어 있음), 나프틸기(탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 아미노기, 탄소수 1 내지 8의 알킬기를 갖는 알킬아미노기 또는 디알킬아미노기에 의해 치환되어 있음), 안트릴기, 피리딜기, 벤조푸릴기, 벤조티에닐기를 나타내고, Ar은 결합이나, 탄소수 1 내지 10의 알킬렌, 비닐렌, 페닐렌, 비페닐렌, 피리딜렌, 나프틸렌, 안트릴렌, 티에닐렌, 푸릴렌, 2,5-피롤-디일, 4,4'-스틸벤-디일, 4,2'-스티렌-디일을 나타내고, n은 0 내지 1의 정수를 나타냄)(In formula, R <1> is a hydrogen atom, a C1-C17 alkyl group, a C1-C8 alkoxy group, a phenyl group, a phenyl group (C1-C17 alkyl group, a C1-C8 alkoxy group, an amino group, C1-C8). Substituted by an alkylamino or dialkylamino group having an alkyl group of 1), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkyl group) Substituted with an amino group), and R 2 and R 3 each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, and a phenyl group (alkyl group having 1 to 17 carbon atoms and carbon atoms). Substituted by an alkylamino group or dialkylamino group having 1 to 8 alkoxy groups, amino groups, alkyl groups having 1 to 8 carbon atoms, and naphthyl groups (alkyl groups having 1 to 17 carbon atoms, 1 carbon atom). And an alkoxy group, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar represents a bond. Alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, anthylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene -Diyl, 4,2'-styrene-diyl, n represents an integer from 0 to 1)
또한, 본 발명의 일 양태의 광경화성 수지 조성물에 있어서, 열경화성 수지를 더 포함하는 것이 바람직하다. 열경화 성분을 함유함으로써 내열성을 더욱 향상시킬 수 있다.Moreover, in the photocurable resin composition of 1 aspect of this invention, it is preferable to further contain a thermosetting resin. By containing a thermosetting component, heat resistance can be improved further.
또한, 본 발명의 일 양태의 광경화성 수지 조성물에 있어서, 착색제를 더 포함하는 것이 바람직하다. 착색제를 함유함으로써 솔더 레지스트로서 바람직하게 사용할 수 있다.Moreover, in the photocurable resin composition of 1 aspect of this invention, it is preferable to contain a coloring agent further. By containing a coloring agent, it can use suitably as a soldering resist.
또한, 본 발명의 일 양태의 광경화성 수지 조성물을 필름 상에 도포, 건조시켜 드라이 필름을 얻을 수 있다. 기재 상에 광경화성 수지 조성물을 도포하지 않고, 용이하게 레지스트층을 형성할 수 있다.Moreover, the dry film can be obtained by apply | coating and drying the photocurable resin composition of one aspect of this invention on a film. A resist layer can be formed easily, without apply | coating a photocurable resin composition on a base material.
또한, 본 발명의 일 양태의 광경화성 수지 조성물을 기재에 도포, 건조하거나, 또는 이것을 필름 상에 도포하여 형성된 드라이 필름을 기재에 라미네이트하고, 활성 에너지선의 조사에 의해 광경화시킴으로써 저에너지 조사이어도 양호한 특성을 갖는 경화물을 얻을 수 있다. 그리고, 경화 시, 또는 리플로우 등의 후속 공정에 있어서, 아웃 가스의 발생에 의한 오염을 억제하는 것이 가능해진다. 또한, 다이렉트 노광 등을 적용함으로써 우수한 위치 정렬 정밀도, 높은 생산성을 갖는 인쇄 배선판을 제공할 수 있다.Moreover, even if it is low energy irradiation by apply | coating and drying the photocurable resin composition of 1 aspect of this invention to a base material, or laminating the dry film formed by apply | coating this on a film to a base material and photocuring by irradiation of an active energy ray, it is a favorable characteristic. Hardened | cured material which has a can be obtained. And it becomes possible to suppress the contamination by generation | occurrence | production of outgas at the time of hardening or in subsequent processes, such as reflow. Further, by applying direct exposure or the like, a printed wiring board having excellent alignment accuracy and high productivity can be provided.
본 발명은 고감도이고, 건조 도막의 지촉 건조성이 우수하고, 경화 시 등의 아웃 가스의 발생을 억제함과 동시에, 예를 들면 인쇄 배선판의 솔더 레지스트를 형성할 때에, 오염을 억제하여, 우수한 위치 정렬 정밀도와 높은 생산성, 신뢰성을 겸비하는 것이 가능한 광경화성 수지 조성물을 제공할 수 있다.The present invention is highly sensitive and excellent in the dryness of the dry coating film, while suppressing generation of outgases during curing and, for example, suppressing contamination when forming a solder resist of a printed wiring board, thereby providing excellent position. The photocurable resin composition which can have alignment precision, high productivity, and reliability can be provided.
이하, 본 발명의 실시 형태에 대해서 상세히 설명한다.Hereinafter, embodiments of the present invention will be described in detail.
본 실시 형태의 광경화성 수지 조성물은 분자 내에 2개의 옥심에스테르기를 갖는 광중합 개시제, 카르복실기 함유 수지, 분자 중에 2개 이상의 에틸렌성 불포화기를 갖는 화합물을 포함하는 것을 특징으로 한다.The photocurable resin composition of this embodiment is characterized by including the photoinitiator which has two oxime ester groups in a molecule | numerator, a carboxyl group-containing resin, and the compound which has two or more ethylenically unsaturated groups in a molecule | numerator.
분자 내에 2개의 옥심에스테르기를 갖는 광중합 개시제를 이용함으로써 고감도의 광경화성 수지 조성물을 얻을 수 있다. 또한, 이것을 경화시킬 때, 또한 리플로우 등의 후속 공정(가열 공정)에 있어서, 아웃 가스의 발생을 억제하는 것이 가능해진다.By using the photoinitiator which has two oxime ester groups in a molecule | numerator, a highly sensitive photocurable resin composition can be obtained. Moreover, when hardening this, it becomes possible to suppress generation | occurrence | production of outgas in further processes (heating process), such as reflow.
상술한 바와 같이, 1분자 내에 1개의 옥심에스테르에 있어서, 아웃 가스의 발생이 어느 정도 억제되지만, 본 실시 형태에서의 광중합 개시제에 따르면, 더욱 아웃 가스의 발생을 억제하는 것이 가능해진다. 이것은, 본 실시 형태에서의 광중합 개시제는 매우 고감도이기 때문에, 적은 첨가량으로도 동등 이상의 감도가 얻어짐과 동시에, 분자 내에 옥심에스테르기를 2개 갖고 있는 것에 의해, 에틸렌성 불포화 이중 결합과 반응할 때에, 가교점으로서 네트워크에 취입되기 때문이라고 생각된다.As mentioned above, although generation | occurrence | production of outgas is suppressed to some extent in one oxime ester in 1 molecule, according to the photoinitiator in this embodiment, it becomes possible to suppress outgas generation further. Since the photoinitiator in this embodiment is very sensitive, even when the addition amount is small, the equivalent or more sensitivity is obtained, and when it reacts with ethylenically unsaturated double bond by having two oxime ester groups in a molecule | numerator, It is considered that it is because it is blown into a network as a bridge | crosslinking point.
즉, 에틸렌성 불포화기를 갖는 카르복실기 함유 수지 또는 에틸렌성 불포화기를 갖는 화합물의 분자 사이에서, 2관능의 관능기로서 반응하는 광해열 분자간 가교형의 광중합 개시제로서 기능하는 것이다.That is, it functions as a photoinitiation crosslinking type photoinitiator which reacts as a bifunctional functional group between the molecule | numerators of carboxyl group-containing resin which has ethylenically unsaturated group, or the compound which has ethylenically unsaturated group.
구체적으로는, 하기 화학식 I로 표시되는 카르바졸 구조를 갖는 옥심에스테르 화합물을 들 수 있다.Specifically, the oxime ester compound which has a carbazole structure represented by following formula (I) is mentioned.
<화학식 I>(I)
(식 중, R1은 수소 원자, 탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 페닐기, 페닐기(탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 아미노기, 탄소수 1 내지 8의 알킬기를 갖는 알킬아미노기 또는 디알킬아미노기에 의해 치환되어 있음), 나프틸기(탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 아미노기, 탄소수 1 내지 8의 알킬기를 갖는 알킬아미노기 또는 디알킬아미노기에 의해 치환되어 있음)를 나타내고, R2, R3은 각각 수소 원자, 탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 할로겐기, 페닐기, 페닐기(탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 아미노기, 탄소수 1 내지 8의 알킬기를 갖는 알킬아미노기 또는 디알킬아미노기에 의해 치환되어 있음), 나프틸기(탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 아미노기, 탄소수 1 내지 8의 알킬기를 갖는 알킬아미노기 또는 디알킬아미노기에 의해 치환되어 있음), 안트릴기, 피리딜기, 벤조푸릴기, 벤조티에닐기를 나타내고, Ar은 결합이나, 탄소수 1 내지 10의 알킬렌, 비닐렌, 페닐렌, 비페닐렌, 피리딜렌, 나프틸렌, 안트릴렌, 티에닐렌, 푸릴렌, 2,5-피롤-디일, 4,4'-스틸벤-디일, 4,2'-스티렌-디일을 나타내고, n은 0 내지 1의 정수를 나타냄)(In formula, R <1> is a hydrogen atom, a C1-C17 alkyl group, a C1-C8 alkoxy group, a phenyl group, a phenyl group (C1-C17 alkyl group, a C1-C8 alkoxy group, an amino group, C1-C8). Substituted by an alkylamino or dialkylamino group having an alkyl group of 1), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkyl group) Substituted with an amino group), and R 2 and R 3 each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, and a phenyl group (alkyl group having 1 to 17 carbon atoms and carbon atoms). Substituted by an alkylamino group or dialkylamino group having 1 to 8 alkoxy groups, amino groups, alkyl groups having 1 to 8 carbon atoms, and naphthyl groups (alkyl groups having 1 to 17 carbon atoms, 1 carbon atom). And an alkoxy group, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar represents a bond. Alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, anthylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene -Diyl, 4,2'-styrene-diyl, n represents an integer from 0 to 1)
이러한 옥심에스테르 화합물을 이용함으로써 더욱 휘발이 감소되어, 아웃 가스에 의한 오염을 억제하는 것이 가능해진다. 이것은, 광 조사에 의한 라디칼 발생(광해열) 개소가 옥심에스테르기이고, 나머지의 카르바졸 2량체는 종래의 광중합 개시제와 비교하여 분자량이 큰 화합물이기 때문이라고 생각된다.By using such an oxime ester compound, volatilization is further reduced and it becomes possible to suppress the contamination by outgas. This is considered to be because the radical generation (photothermal heat) point by light irradiation is an oxime ester group, and the remaining carbazole dimer is a compound with a large molecular weight compared with the conventional photoinitiator.
또한, 화학식 I 중, R1, R2가 각각 메틸기 또는 에틸기이고, R3은 메틸 또는 페닐이고, Ar은 결합이나, 페닐렌, 나프틸렌 또는 티에닐렌, n은 0인 것이 바람직하다.In formula (I), R 1 and R 2 are each a methyl group or an ethyl group, R 3 is methyl or phenyl, Ar is a bond, phenylene, naphthylene or thienylene, and n is preferably 0.
이러한 광중합 개시제의 배합량으로서는 카르복실기 함유 수지 100 중량부에 대하여 0.01 내지 5 중량부인 것이 바람직하고, 5 중량부보다 많으면 광의 흡수가 많아지고, 레지스트 바닥부의 광 반응성이 저하되어 언더컷이 생김과 동시에, 지촉 건조성이 악화한다. 한편, 0.01 중량부 미만이면 구리 상에서의 광경화성이 부족하여, 도막이 박리함과 함께, 내약품성 등의 도막 특성이 저하된다. 더욱 바람직하게는 0.1 내지 3 중량부이다.As a compounding quantity of such a photoinitiator, it is preferable that it is 0.01-5 weight part with respect to 100 weight part of carboxyl group-containing resin, and when it is more than 5 weight part, light absorption will increase, the photoreactivity of a resist bottom part will fall, an undercut will occur, and a touch key will dry. The composition worsens. On the other hand, when it is less than 0.01 weight part, the photocurability on copper will be inadequate, peeling a coating film and coating film characteristics, such as chemical-resistance, will fall. More preferably, it is 0.1-3 weight part.
본 실시 형태의 광경화성 수지 조성물에 있어서의 카르복실기 함유 수지는 알칼리 현상성을 부여하기 위해서 이용되고, 분자 중에 카르복실기를 함유하는 공지된 수지를 사용할 수 있다. 특히, 광경화성이나 내현상성의 면에서, 분자 중에 에틸렌성 불포화 이중 결합을 갖는 카르복실기 함유 수지가 바람직하다. 그리고, 그 불포화 이중 결합은 아크릴산 또는 메타크릴산, 또는 이들의 유도체 유래인 것이 보다 바람직하다. 이하에 구체예를 나타낸다.The carboxyl group-containing resin in the photocurable resin composition of this embodiment is used in order to provide alkali developability, and well-known resin which contains a carboxyl group in a molecule | numerator can be used. In particular, in view of photocurability and developability, a carboxyl group-containing resin having an ethylenically unsaturated double bond in the molecule is preferable. The unsaturated double bond is more preferably derived from acrylic acid or methacrylic acid, or derivatives thereof. Specific examples are shown below.
(1) (메트)아크릴산 등의 불포화 카르복실산과, 스티렌, α-메틸스티렌, 저급 알킬(메트)아크릴레이트, 이소부틸렌 등의 불포화기 함유 화합물과의 공중합에 의해 얻어지는 카르복실기 함유 수지.(1) Carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and unsaturated group containing compounds, such as styrene, (alpha) -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
(2) 지방족 디이소시아네이트, 분지 지방족 디이소시아네이트, 지환식 디이소시아네이트, 방향족 디이소시아네이트 등의 디이소시아네이트와, 디메틸올프로피온산, 디메틸올부탄산 등의 카르복실기 함유 디알코올 화합물 및 폴리카보네이트계 폴리올, 폴리에테르계 폴리올, 폴리에스테르계 폴리올, 폴리올레핀계 폴리올, 아크릴계 폴리올, 비스페놀 A계 알킬렌옥시드 부가체 디올, 페놀성 히드록실기 및 알코올성 히드록실기를 갖는 화합물 등의 디올 화합물의 중부가 반응에 의한 카르복실기 함유 우레탄 수지.(2) a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate and an aromatic diisocyanate, a dialcohol compound containing a carboxyl group such as dimethylolpropionic acid and dimethylolbutanoic acid, and a polycarbonate polyol, a polyether polyol Containing urethane resin obtained by a mid-portion reaction of a diol compound such as a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group .
(3) 지방족 디이소시아네이트, 분지 지방족 디이소시아네이트, 지환식 디이소시아네이트, 방향족 디이소시아네이트 등의 디이소시아네이트 화합물과, 폴리카보네이트계 폴리올, 폴리에테르계 폴리올, 폴리에스테르계 폴리올, 폴리올레핀계 폴리올, 아크릴계 폴리올, 비스페놀 A계 알킬렌옥시드 부가체 디올, 페놀성 히드록실기 및 알코올성 히드록실기를 갖는 화합물 등의 디올 화합물의 중부가 반응에 의한 우레탄 수지의 말단에 산무수물을 반응시켜 이루어지는 말단 카르복실기 함유 우레탄 수지.(3) diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A terminal carboxyl group-containing urethane resin formed by making an acid anhydride react with the terminal of the urethane resin by polyaddition reaction of diol compounds, such as A type alkylene oxide adduct diol, a compound which has a phenolic hydroxyl group, and alcoholic hydroxyl group.
(4) 디이소시아네이트와, 비스페놀 A형 에폭시 수지, 수소 첨가 비스페놀 A형 에폭시 수지, 비스페놀 F형 에폭시 수지, 비스페놀 S형 에폭시 수지, 비크실레놀형 에폭시 수지, 비페놀형 에폭시 수지 등의 2관능 에폭시 수지의 (메트)아크릴레이트 또는 그의 부분 산무수물 변성물, 카르복실기 함유 디알코올 화합물 및 디올 화합물의 중부가 반응에 의한 카르복실기 함유 감광성 우레탄 수지.(4) bifunctional epoxy resins such as diisocyanate, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin The carboxyl group-containing photosensitive urethane resin by the polyaddition reaction of the (meth) acrylate or its partial acid anhydride modified | denatured product, a carboxyl group-containing dialcohol compound, and a diol compound.
(5) 상술한 (2) 또는 (4)의 수지의 합성 중에 히드록시알킬(메트)아크릴레이트 등의 분자 중에 1개의 수산기와 1개 이상의 (메트)아크릴로일기를 갖는 화합물을 가하여 말단(메트)아크릴화한 카르복실기 함유 우레탄 수지.(5) During the synthesis of the resin of (2) or (4) described above, a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added to the terminal (meth ) Acrylicated carboxyl group-containing urethane resin.
(6) 상술한 (2) 또는 (4)의 수지의 합성 중에 이소포론디이소시아네이트와 펜타에리트리톨트리아크릴레이트의 등몰 반응물 등, 분자 중에 1개의 이소시아네이트기와 1개 이상의 (메트)아크릴로일기를 갖는 화합물을 가하여 말단(메트)아크릴화한 카르복실기 함유 우레탄 수지.(6) Having one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate during synthesis of the resin of (2) or (4) above The carboxyl group-containing urethane resin which added the compound and was terminal (meth) acrylated.
(7) 후술하는 2관능 또는 그 이상의 다관능(고형) 에폭시 수지에 (메트)아크릴산을 반응시켜, 측쇄에 존재하는 수산기에 무수프탈산, 테트라히드로무수프탈산, 헥사히드로무수프탈산 등의 2염기산 무수물을 부가시킨 카르복실기 함유 감광성 수지.(7) (meth) acrylic acid is made to react with the bifunctional or more than one polyfunctional (solid) epoxy resin mentioned later, and dibasic acid anhydrides, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, to the hydroxyl group which exists in a side chain. Carboxyl group containing photosensitive resin which added this.
(8) 후술하는 2관능(고형) 에폭시 수지의 수산기를 추가로 에피클로로히드린으로 에폭시화한 다관능 에폭시 수지에 (메트)아크릴산을 반응시키고, 생성된 수산기에 2염기산 무수물을 부가시킨 카르복실기 함유 감광성 수지.(8) A carboxyl group in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin further epoxidized with epichlorohydrin, to which a hydroxyl group of a bifunctional (solid) epoxy resin described later is added, and a dibasic anhydride is added to the resulting hydroxyl group. Containing photosensitive resin.
(9) 노볼락 등의 다관능 페놀 화합물에 에틸렌옥시드 등의 환상 에테르, 프로필렌카보네이트 등의 환상 카보네이트를 부가시키고, 얻어진 수산기를 (메트)아크릴산으로 부분 에스테르화하고, 나머지의 수산기에 다염기산 무수물을 반응시킨 카르복실기 함유 감광성 수지.(9) Cyclic carbonates, such as cyclic ethers, such as ethylene oxide, and a propylene carbonate, are added to polyfunctional phenol compounds, such as novolak, and the obtained hydroxyl group is partially esterified by (meth) acrylic acid, and a polybasic acid anhydride is made to the remaining hydroxyl group. The carboxyl group-containing photosensitive resin made to react.
(10) 이들 (1) 내지 (9)의 수지에, 추가로 글리시딜(메트)아크릴레이트, α-메틸글리시딜(메트)아크릴레이트 등의 분자 중에 1개의 에폭시기와 1개 이상의 (메트)아크릴로일기를 갖는 화합물을 부가하여 이루어지는 카르복실기 함유 감광성 수지.(10) To these resins (1) to (9), one epoxy group and one or more (meth) groups in a molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, etc. Carboxyl group-containing photosensitive resin formed by adding the compound which has a) acryloyl group.
이러한 카르복실기 함유 수지는 이들로 한하지 않고 사용할 수 있고, 1 종이거나 복수종 혼합해서도 사용할 수 있다.Such carboxyl group-containing resin can be used not only in these, but can also be used 1 type or in mixture of multiple types.
또한, 여기서 (메트)아크릴레이트란 아크릴레이트, 메타크릴레이트 및 이들의 혼합물을 총칭하는 용어로서, 이하 다른 유사의 표현에 대해서도 동일하다.In addition, (meth) acrylate is a term used here generically for an acrylate, a methacrylate, and a mixture thereof, The same also about the expression of another similarity hereafter.
이러한 카르복실기 함유 수지에 의해, 백본 중합체의 측쇄에 다수의 유리의 카르복실기를 갖기 때문에, 희알칼리 수용액에 의한 현상이 가능해진다.Since such carboxyl group-containing resin has many glass carboxyl groups in the side chain of a backbone polymer, image development by a rare alkali aqueous solution is attained.
또한, 이러한 카르복실기 함유 수지의 산가는 40 내지 200 mgKOH/g이다. 카르복실기 함유 수지의 산가가 40 mgKOH/g 미만이면 알칼리 현상이 곤란해지고, 한편 200 mgKOH/g을 초과하면 현상액에 의한 노광부의 용해가 진행하기 때문에, 필요 이상으로 라인이 가늘어지고, 경우에 따라서는 노광부와 미노광부의 구별없이 현상액으로 용해 박리하게 되어, 정상적인 레지스트 패턴의 묘화가 곤란해진다. 보다 바람직하게는 45 내지 120 mgKOH/g이다.In addition, the acid value of such carboxyl group-containing resin is 40-200 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary, and in some cases, the furnace It dissolves and peels with a developing solution without distinguishing a light part and an unexposed part, and drawing of a normal resist pattern becomes difficult. And more preferably 45 to 120 mgKOH / g.
또한, 이러한 카르복실기 함유 수지의 중량 평균 분자량은 수지 골격에 따라 다르지만, 일반적으로 2,000 내지 150,000인 것이 바람직하다. 중량 평균 분자량이 2,000 미만이면 태크프리 성능이 떨어지는 경우가 있고, 노광 후의 도막의 내습성이 나쁘고, 현상 시에 막감소가 생기고, 해상도가 크게 떨어지는 경우가 있다. 한편, 중량 평균 분자량이 150,000을 초과하면 현상성이 현저히 나빠지는 경우가 있고, 저장 안정성이 열화하는 경향이 있다. 보다 바람직하게는 5,000 내지 100,000이다.Moreover, although the weight average molecular weight of such carboxyl group-containing resin changes with resin skeleton, it is preferable that it is generally 2,000-150,000. If the weight average molecular weight is less than 2,000, the tack-free performance may be inferior, the moisture resistance of the coating film after exposure is bad, a film reduction may occur at the time of image development, and the resolution may fall large. On the other hand, when a weight average molecular weight exceeds 150,000, developability may become remarkably bad and there exists a tendency for storage stability to deteriorate. More preferably from 5,000 to 100,000.
이러한 카르복실기 함유 수지의 배합량은 광경화성 수지 조성물 중에 20 내지 80 질량%가 적당하다. 20 질량% 미만이면 피막 강도가 저하된다. 한편 60 질량% 보다 많은 경우, 조성물의 점성이 높아져서 도포성 등이 저하된다. 보다 바람직하게는 30 내지 60 질량%이다.As for the compounding quantity of such carboxyl group-containing resin, 20-80 mass% is suitable in a photocurable resin composition. If it is less than 20 mass%, film strength will fall. On the other hand, when more than 60 mass%, the viscosity of a composition becomes high and applicability | paintability etc. fall. And more preferably 30 to 60 mass%.
본 실시 형태의 광경화성 수지 조성물에 있어서의, 분자 중에 2개 이상의 에틸렌성 불포화기를 갖는 화합물은 활성 에너지선 조사에 의해 광경화하여, 카르복실기 함유 수지를 알칼리 수용액에 불용화하거나, 또는 불용화를 돕기 위해서 이용된다.In the photocurable resin composition of this embodiment, the compound which has 2 or more ethylenically unsaturated groups in a molecule | numerator is photocured by active energy ray irradiation, and insolubilizes carboxyl group-containing resin in aqueous alkali solution, or helps insolubilization. It is used for
이러한 화합물로서는 에틸렌글리콜, 메톡시테트라에틸렌글리콜, 폴리에틸렌글리콜, 프로필렌글리콜 등의 글리콜의 디아크릴레이트류; 헥산디올, 트리메틸올프로판, 펜타에리트리톨, 디펜타에리트리톨, 트리스-히드록시에틸이소시아누레이트 등의 다가 알코올 또는 이들의 에틸렌옥시드 부가물 또는 프로필렌옥시드 부가물 등의 다가 아크릴레이트류; 페녹시아크릴레이트, 비스페놀 A 디아크릴레이트, 및 이들의 페놀류의 에틸렌옥시드 부가물 또는 프로필렌옥시드 부가물 등의 다가 아크릴레이트류; 글리세린디글리시딜에테르, 글리세린트리글리시딜에테르, 트리메틸올프로판트리글리시딜에테르, 트리글리시딜이소시아누레이트 등의 글리시딜에테르의 다가 아크릴레이트류; 및 우레탄아크릴레이트, 멜라민아크릴레이트, 및/또는 이들 아크릴레이트에 대응하는 각 메타크릴레이트류 등을 들 수 있다.As such a compound, Diacrylates of glycol, such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, propylene glycol; Polyhydric acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts or propylene oxide adducts thereof; Polyhydric acrylates, such as ethylene oxide adduct or propylene oxide adduct of phenoxy acrylate, bisphenol A diacrylate, and these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; And urethane acrylate, melamine acrylate, and / or respective methacrylates corresponding to these acrylates.
또한, 크레졸노볼락형 에폭시 수지 등의 다관능 에폭시 수지에 아크릴산을 반응시킨 에폭시아크릴레이트 수지나, 또한 그 에폭시아크릴레이트 수지의 수산기에 펜타에리트리톨트리아크릴레이트 등의 히드록시아크릴레이트와 이소포론디이소시아네이트 등의 디이소시아네이트의 하프우레탄 화합물을 반응시킨 에폭시우레탄아크릴레이트 화합물 등을 들 수 있다. 이러한 에폭시아크릴레이트계 수지는 지촉 건조성을 저하시키지 않고 광경화성을 향상시킬 수 있다.Further, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as a cresol novolak type epoxy resin with acrylic acid, or an epoxy acrylate resin obtained by reacting a hydroxy acrylate such as pentaerythritol triacrylate with an isophorone di And an epoxy urethane acrylate compound obtained by reacting a half urethane compound of a diisocyanate such as isocyanate. Such an epoxy acrylate resin can improve photo-curability without lowering the touch-dry composition.
이러한 화합물의 배합량은 카르복실기 함유 수지 100 질량부에 대하여 5 내지 100 질량부인 것이 바람직하다. 5 질량부 미만인 경우, 광경화성이 저하되어, 활성 에너지선 조사후의 알칼리 현상에 의해 패턴 형성이 곤란해진다. 한편, 100 질량부를 초과한 경우, 알칼리 수용액에 대한 용해성이 저하되어, 도막이 취약해진다. 보다 바람직하게는 1 내지 70 질량부이다.It is preferable that the compounding quantity of such a compound is 5-100 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When less than 5 mass parts, photocurability falls and pattern formation becomes difficult by alkali image development after active energy ray irradiation. On the other hand, if it exceeds 100 parts by mass, the solubility in an aqueous alkali solution is lowered and the coating film becomes weak. More preferably 1 to 70 parts by mass.
본 실시 형태의 광경화성 수지 조성물에 있어서, 아울러 상술한 분자 내에 2개의 옥심에스테르기를 갖는 광중합 개시제 이외의 광중합 개시제를 사용할 수 있다.In the photocurable resin composition of this embodiment, photoinitiators other than the photoinitiator which has two oxime ester groups in the molecule mentioned above can also be used.
예를 들면, 1분자 내에 1개의 옥심에스테르기를 갖는 옥심에스테르계 광중합 개시제, α-아미노아세토페논계 광중합 개시제, 아실포스핀옥시드계 광중합 개시제로 이루어지는 군에서 선택되는 1종 이상의 광중합 개시제를 사용할 수 있다.For example, one or more photoinitiators selected from the group consisting of an oxime ester photoinitiator having one oxime ester group in one molecule, an α-aminoacetophenone photoinitiator and an acylphosphine oxide photoinitiator can be used. .
옥심에스테르계 광중합 개시제로서는, 시판품으로서 바스프(BASF) 재팬사 제조의 CGI-325, 이르가큐어(등록상표) OXE01, 이르가큐어 OXE02, 아데카(ADEKA)사 제조의 N-1919 등을 들 수 있다. 이들 옥심에스테르계 광중합 개시제는 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.Examples of the oxime ester photopolymerization initiator include CGI-325 manufactured by BASF Japan, Irgacure (registered trademark) OXE01, Irgacure OXE02, and N-1919 manufactured by Adeka Co., Ltd. have. These oxime ester-based photopolymerization initiators may be used alone or in combination of two or more.
이러한 옥심에스테르계 광중합 개시제의 배합량은 카르복실기 함유 수지 100 질량부에 대하여 0.01 내지 5 질량부로 하는 것이 바람직하다. 0.01 질량부 미만이면 구리 상에서의 광경화성이 부족하여, 도막이 박리함과 함께, 내약품성 등의 도막 특성이 저하된다. 한편, 5 질량부를 초과하면 아웃 가스의 감소 효과가 얻어지지 않고, 또한 솔더 레지스트 도막 표면에서의 광흡수가 심해져서, 심부 경화성이 저하되는 경향이 있다. 보다 바람직하게는 0.5 내지 3 질량부이다.It is preferable that the compounding quantity of such an oxime ester type photoinitiator shall be 0.01-5 mass parts with respect to 100 mass parts of carboxyl group-containing resin. If it is less than 0.01 mass part, the photocurability on copper will run out, peeling a coating film and coating film characteristics, such as chemical-resistance, will fall. On the other hand, when it exceeds 5 mass parts, the effect of reducing outgas will not be acquired, and the light absorption on the surface of a soldering resist coating will become deep, and there exists a tendency for deep-curing property to fall. More preferably, it is 0.5-3 mass parts.
α-아미노아세토페논계 광중합 개시제로서는, 구체적으로는 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로파논-1, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-부탄-1-온, 2-(디메틸아미노)-2-[(4-메틸페닐)메틸]-1-[4-(4-모르폴리닐)페닐]-1-부타논, N,N-디메틸아미노아세토페논 등을 들 수 있다. 시판품으로서는 바스프 재팬사 제조의 이르가큐어907, 이르가큐어369, 이르가큐어379 등을 들 수 있다.Specific examples of the? -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone, N, N-dimethylaminoacetophenone, and the like. Examples of commercially available products include Irgacure 907, Irgacure 369 and Irgacure 379 manufactured by BASF Japan.
아실포스핀옥시드계 광중합 개시제로서는, 구체적으로는 2,4,6-트리메틸벤조일디페닐포스핀옥시드, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥시드, 비스(2,6-디메톡시벤조일)-2,4,4-트리메틸-펜틸포스핀옥시드 등을 들 수 있다. 시판품으로서는 바스프사 제조의 루시린 TPO, 바스프 재팬사 제조의 이르가큐어819 등을 들 수 있다.As an acyl phosphine oxide type photoinitiator, 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, bis (2, 4, 6- trimethyl benzoyl)-phenyl phosphine oxide, bis (2, 6- dime specifically, Oxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like. Examples of commercially available products include Lucirin TPO manufactured by BASF Corporation, Irgacure 819 manufactured by BASF Japan Corporation.
이들 α-아미노아세토페논계 광중합 개시제, 아실포스핀옥시드계 광중합 개시제의 배합량은 카르복실기 함유 수지 100 질량부에 대하여 0.01 내지 15 질량부인 것이 바람직하다. 0.01 질량부 미만이면 마찬가지로 구리 상에서의 광경화성이 부족하여, 도막이 박리함과 함께, 내약품성 등의 도막 특성이 저하된다. 한편, 15 질량부를 초과하면 아웃 가스의 감소 효과가 얻어지지 않고, 또한 솔더 레지스트 도막 표면에서의 광흡수가 심해져서, 심부 경화성이 저하되는 경향이 있다. 보다 바람직하게는 0.5 내지 10 질량부이다.It is preferable that the compounding quantity of these (alpha)-amino acetophenone type photoinitiators and an acyl phosphine oxide type photoinitiators is 0.01-15 mass parts with respect to 100 mass parts of carboxyl group-containing resin. If it is less than 0.01 mass part, similarly, the photocurability on copper will be inferior, the coating film will peel, and coating film characteristics, such as chemical-resistance, will fall. On the other hand, when it exceeds 15 mass parts, the effect of reducing outgas will not be acquired, and the light absorption on the surface of a soldering resist coating will become deep, and there exists a tendency for deep-curing property to fall. More preferably 0.5 to 10 parts by mass.
기타, 본 실시 형태의 광경화성 수지 조성물에 바람직하게 사용할 수 있는 광중합 개시제, 광 개시 보조제 및 증감제로서는 벤조인 화합물, 아세토페논 화합물, 안트라퀴논 화합물, 티오크산톤 화합물, 케탈 화합물, 벤조페논 화합물, 3급 아민 화합물 및 크산톤 화합물 등을 들 수 있다.In addition, as a photoinitiator, a photoinitiator, and a sensitizer which can be used suitably for the photocurable resin composition of this embodiment, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, Tertiary amine compounds, xanthone compounds and the like.
벤조인 화합물로서는, 구체적으로는 예를 들면 벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인이소프로필에테르 등을 들 수 있다.Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.
아세토페논 화합물로서는, 구체적으로는 예를 들면 아세토페논, 2,2-디메톡시-2-페닐아세토페논, 2,2-디에톡시-2-페닐아세토페논, 1,1-디클로로아세토페논 등을 들 수 있다.Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone. .
안트라퀴논 화합물로서는, 구체적으로는 예를 들면 2-메틸안트라퀴논, 2-에틸안트라퀴논, 2-t-부틸안트라퀴논, 1-클로로안트라퀴논 등을 들 수 있다.Specific examples of the anthraquinone compound include 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthraquinone.
티오크산톤 화합물로서는, 구체적으로는 예를 들면 2,4-디메틸티오크산톤, 2,4-디에틸티오크산톤, 2-클로로티오크산톤, 2,4-디이소프로필티오크산톤 등을 들 수 있다.Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and the like. .
케탈 화합물로서는, 구체적으로는 예를 들면 아세토페논디메틸케탈, 벤질디메틸케탈 등을 들 수 있다.Specific examples of the ketal compound include acetophenone dimethyl ketal, benzyl dimethyl ketal, and the like.
벤조페논 화합물로서는, 구체적으로는 예를 들면 벤조페논, 4-벤조일디페닐술피드, 4-벤조일-4'-메틸디페닐술피드, 4-벤조일-4'-에틸디페닐술피드, 4-벤조일-4'-프로필디페닐술피드 등을 들 수 있다.Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl- Benzoyl-4'-propyldiphenyl sulfide and the like.
3급 아민 화합물로서는, 구체적으로는 예를 들면 에탄올아민 화합물, 디알킬아미노벤젠 구조를 갖는 화합물, 예를 들면 시판품으로서는 4,4'-디메틸아미노벤조페논(니혼소다사 제조의 닛소큐어(등록상표) MABP), 4,4'-디에틸아미노벤조페논(호도가야 가가꾸사 제조의 EAB) 등의 디알킬아미노벤조페논, 7-(디에틸아미노)-4-메틸-2H-1-벤조피란-2-온(7-(디에틸아미노)-4-메틸쿠마린) 등의 디알킬아미노기 함유 쿠마린 화합물, 4-디메틸아미노벤조산에틸(닛본 가야꾸사 제조의 가야큐어(등록상표) EPA), 2-디메틸아미노벤조산에틸(인터내셔날바이오-신세틱스사 제조의 퀀타큐어(Quantacure) DMB), 4-디메틸아미노벤조산(n-부톡시)에틸(인터내셔날바이오-신세틱스사 제조의 퀀타큐어 BEA), p-디메틸아미노벤조산이소아밀에틸에스테르(닛본 가야꾸사 제조의 가야큐어 DMBI), 4-디메틸아미노벤조산 2-에틸헥실(반 다이크(Van Dyk)사 제조의 에솔롤(Esolol) 507), 4,4'-디에틸아미노벤조페논(호도가야 가가꾸사 제조의 EAB) 등을 들 수 있다.Specifically as a tertiary amine compound, For example, an ethanolamine compound and the compound which has a dialkylaminobenzene structure, For example, as a commercial item 4,4'- dimethylamino benzophenone (Nissocure (made by Nippon Soda Co., Ltd.) Dialkylaminobenzophenone, 7- (diethylamino) -4-methyl-2H-1-benzopyran, such as MABP) and 4,4'-diethylaminobenzophenone (EAB by Hodogaya Chemical Co., Ltd.). Dialkylamino group-containing coumarin compounds such as 2-one (7- (diethylamino) -4-methylcoumarin), ethyl 4-dimethylaminobenzoate (Gayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), 2- Ethyl dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics Co., Ltd.), p-dimethyl Aminobenzoic acid isoamyl ethyl ester (Gayacure DMBI by Nippon Kayaku Co., Ltd.), 4-di 2-ethylhexyl (Esolol 507 by Van Dyk), 4,4'- diethylamino benzophenone (EAB by Hodogaya Chemical Co., Ltd.) etc. are mentioned. .
이들 중에서, 티오크산톤 화합물 및 3급 아민 화합물이 바람직하다. 특히, 티오크산톤 화합물이 포함되는 것이 심부 경화성의 면에서 바람직하다. 그 중에서도, 2,4-디메틸티오크산톤, 2,4-디에틸티오크산톤, 2-클로로티오크산톤, 2,4-디이소프로필티오크산톤 등의 티오크산톤 화합물을 포함하는 것이 바람직하다.Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, it is preferable to contain a thioxanthone compound from the point of deep-hardening property. Especially, it is preferable to contain thioxanthone compounds, such as 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, and 2, 4- diisopropyl thioxanthone. Do.
이러한 티오크산톤 화합물의 배합량으로서는 카르복실기 함유 수지 100 질량부에 대하여 20 질량부 이하인 것이 바람직하다. 티오크산톤 화합물의 배합량이 20 질량부를 초과하면 후막 경화성이 저하함과 함께, 제품의 비용 상승으로 이어진다. 보다 바람직하게는 10 질량부 이하이다.As a compounding quantity of such a thioxanthone compound, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of carboxyl group-containing resin. When the compounding quantity of a thioxanthone compound exceeds 20 mass parts, thick film sclerosis | hardenability will fall and it will lead to the cost increase of a product. More preferably 10 parts by mass or less.
또한, 3급 아민 화합물로서는 디알킬아미노벤젠 구조를 갖는 화합물이 바람직하고, 그 중에서도 디알킬아미노벤조페논 화합물, 최대 흡수 파장이 350 내지 450 nm에 있는 디알킬아미노기 함유 쿠마린 화합물 및 케토쿠마린류가 특히 바람직하다.As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable. Among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, Particularly preferred.
디알킬아미노벤조페논 화합물로서는 4,4'-디에틸아미노벤조페논이 독성도 낮아 바람직하다. 디알킬아미노기 함유 쿠마린 화합물은 최대 흡수 파장이 350 내지 410 nm로 자외선 영역에 있기 때문에, 착색이 적고, 무색 투명의 감광성 조성물은 물론, 착색 안료를 이용하여, 착색 안료 자체의 색을 반영한 착색 솔더 레지스트막을 제공하는 것이 가능해진다. 특히, 7-(디에틸아미노)-4-메틸-2H-1-벤조피란-2-온이 파장 400 내지 410 nm의 레이저광에 대하여 우수한 증감 효과를 나타내는 것으로부터 바람직하다.As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is also preferable because of its low toxicity. Since the dialkylamino group-containing coumarin compound is in the ultraviolet region with a maximum absorption wavelength of 350 to 410 nm, the coloring solder resist reflects the color of the colored pigment itself using a color pigment, as well as a colorless and transparent photosensitive composition. It is possible to provide a membrane. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it shows the excellent sensitizing effect with respect to the laser beam of wavelength 400-410 nm.
이러한 3급 아민 화합물의 배합량으로서는 카르복실기 함유 수지 100 질량부에 대하여 0.1 내지 20 질량부인 것이 바람직하다. 3급 아민 화합물의 배합량이 0.1 질량부 미만이면 충분한 증감 효과를 얻을 수 없는 경향이 있다. 20 질량부를 초과하면 3급 아민 화합물에 의한 건조 솔더 레지스트 도막의 표면에서의 광흡수가 심해져서, 심부 경화성이 저하되는 경향이 있다. 보다 바람직하게는 0.1 내지 10 질량부이다.As a compounding quantity of such a tertiary amine compound, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When the compounding quantity of a tertiary amine compound is less than 0.1 mass part, there exists a tendency for sufficient sensitization effect not to be acquired. If the amount is more than 20 parts by mass, the light absorption at the surface of the dried solder resist coating film by the tertiary amine compound becomes severe, and the deep portion curing property tends to be lowered. More preferably 0.1 to 10 parts by mass.
이들 광중합 개시제, 광 개시 보조제 및 증감제는 단독으로 또는 2종 이상의 혼합물로서 사용할 수 있다.These photoinitiators, photoinitiation aids, and sensitizers can be used alone or as a mixture of two or more thereof.
이러한 광중합 개시제, 광 개시 보조제 및 증감제의 총량은 상기 카르복실산 함유 수지 100 질량부에 대하여 35 질량부 이하인 것이 바람직하다. 35 질량부를 초과하면 이들의 광흡수에 의해 심부 경화성이 저하되는 경향이 있다.It is preferable that the total amount of such a photoinitiator, a photoinitiator, and a sensitizer is 35 mass parts or less with respect to 100 mass parts of said carboxylic acid containing resins. When it exceeds 35 mass parts, there exists a tendency for deep-part sclerosis | hardenability to fall by these light absorption.
또한, 이들 광중합 개시제, 광 개시 보조제 및 증감제는 특정한 파장을 흡수하기 때문에, 경우에 따라서는 감도가 낮아져, 자외선 흡수제로서 기능하는 경우가 있다. 그러나, 이들은 조성물의 감도를 향상시키는 것만의 목적으로 이용되는 것이 아니다. 필요에 따라서 특정한 파장의 광을 흡수시켜, 표면의 광 반응성을 높여, 레지스트의 라인 형상 및 개구를 수직, 테이퍼상, 역테이퍼상으로 변화시킴과 동시에, 라인폭이나 개구경의 가공 정밀도를 향상시킬 수 있다.Moreover, since these photoinitiators, a photoinitiation adjuvant, and a sensitizer absorb a specific wavelength, in some cases, a sensitivity becomes low and may function as a ultraviolet absorber. However, they are not used for the purpose of improving the sensitivity of the composition. By absorbing light of a specific wavelength as needed, it improves the light reactivity of the surface, and changes the line shape and opening of the resist into vertical, tapered and inverse tapered shapes, and improves the processing accuracy of the line width and the opening diameter. Can be.
본 실시 형태의 광경화성 수지 조성물에는 감도를 향상시키기 위해서 연쇄 이동제로서 공지된 N 페닐글리신류, 페녹시아세트산류, 티오페녹시아세트산류, 머캅토티아졸 등을 사용할 수 있다.In order to improve a sensitivity, the photocurable resin composition of this embodiment can use N phenylglycine, phenoxy acetic acid, thiophenoxy acetic acid, mercaptothiazole, etc. which are well-known as a chain transfer agent.
구체적으로는, 예를 들면 머캅토숙신산, 머캅토아세트산, 머캅토프로피온산, 메티오닌, 시스테인, 티오살리실산 및 그의 유도체 등의 카르복실기를 갖는 연쇄 이동제; 머캅토에탄올, 머캅토프로판올, 머캅토부탄올, 머캅토프로판디올, 머캅토부탄디올, 히드록시벤젠티올 및 그의 유도체 등의 수산기를 갖는 연쇄 이동제; 1-부탄티올, 부틸-3-머캅토프로피오네이트, 메틸-3-머캅토프로피오네이트, 2,2-(에틸렌디옥시)디에탄티올, 에탄티올, 4-메틸벤젠티올, 도데실머캅탄, 프로판티올, 부탄티올, 펜탄티올, 1-옥탄티올, 시클로펜탄티올, 시클로헥산티올, 티오글리세롤, 4,4-티오비스벤젠티올 등을 들 수 있다.Specifically, For example, Chain transfer agent which has carboxyl groups, such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and its derivative (s); Chain transfer agents having a hydroxyl group such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropane diol, mercaptobutanediol, hydroxybenzene thiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecylmercaptan , Propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like.
또한, 다관능성 머캅탄계 화합물을 사용할 수 있고, 구체적으로는 예를 들면 헥산-1,6-디티올, 데칸-1,10-디티올, 디머캅토디에틸에테르, 디머캅토디에틸술피드 등의 지방족 티올류, 크실릴렌디머캅탄, 4,4'-디머캅토디페닐술피드, 1,4-벤젠디티올 등의 방향족 티올류; 에틸렌글리콜비스(머캅토아세테이트), 폴리에틸렌글리콜비스(머캅토아세테이트), 프로필렌글리콜비스(머캅토아세테이트), 글리세린트리스(머캅토아세테이트), 트리메틸올에탄트리스(머캅토아세테이트), 트리메틸올프로판트리스(머캅토아세테이트), 펜타에리트리톨테트라키스(머캅토아세테이트), 디펜타에리트리톨헥사키스(머캅토아세테이트) 등의 다가 알코올의 폴리(머캅토아세테이트)류; 에틸렌글리콜비스(3-머캅토프로피오네이트), 폴리에틸렌글리콜비스(3-머캅토프로피오네이트), 프로필렌글리콜비스(3-머캅토프로피오네이트), 글리세린트리스(3-머캅토프로피오네이트), 트리메틸올에탄트리스(머캅토프로피오네이트), 트리메틸올프로판트리스(3-머캅토프로피오네이트), 펜타에리트리톨테트라키스(3-머캅토프로피오네이트), 디펜타에리트리톨헥사키스(3-머캅토프로피오네이트) 등의 다가 알코올의 폴리(3-머캅토프로피오네이트)류; 1,4-비스(3-머캅토부티릴옥시)부탄, 1,3,5-트리스(3-머캅토부틸옥시에틸)-1,3,5-트리아진-2,4,6(1H,3H,5H)-트리온, 펜타에리트리톨테트라키스(3-머캅토부티레이트) 등의 폴리(머캅토부티레이트)류 등을 들 수 있다.Moreover, a polyfunctional mercaptan type compound can be used, Specifically, such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethyl sulfide, etc. Aromatic thiols such as aliphatic thiols, xylylenedimercaptan, 4,4'-dimercaptodiphenylsulfide, and 1,4-benzenedithiol; (Mercaptoacetate), ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylol ethane tris Poly (mercaptoacetates) of polyhydric alcohols such as mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), dipentaerythritol hexakis (mercaptoacetate); (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate) , Trimethylol ethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis - mercapto propionate); poly (3-mercaptopropionates) of polyhydric alcohols; 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- 3H, 5H) -triene, and poly (mercaptobutyrates) such as pentaerythritol tetrakis (3-mercaptobutyrate).
또한, 머캅토기를 갖는 복소환 화합물을 사용할 수 있고, 구체적으로는 예를 들면 머캅토-4-부티로락톤(별칭: 2-머캅토-4-부타놀리드), 2-머캅토-4-메틸-4-부티로락톤, 2-머캅토-4-에틸-4-부티로락톤, 2-머캅토-4-부틸로티오락톤, 2-머캅토-4-부티로락탐, N-메톡시-2-머캅토-4-부티로락탐, N-에톡시-2-머캅토-4-부티로락탐, N-메틸-2-머캅토-4-부티로락탐, N-에틸-2-머캅토-4-부티로락탐, N-(2-메톡시)에틸-2-머캅토-4-부티로락탐, N-(2-에톡시)에틸-2-머캅토-4-부티로락탐, 2-머캅토-5-발레로락톤, 2-머캅토-5-발레로락탐, N-메틸-2-머캅토-5-발레로락탐, N-에틸-2-머캅토-5-발레로락탐, N-(2-메톡시)에틸-2-머캅토-5-발레로락탐, N-(2-에톡시)에틸-2-머캅토-5-발레로락탐 및 2-머캅토-6-헥사노락탐 등을 들 수 있다.Moreover, the heterocyclic compound which has a mercapto group can be used, For example, mercapto-4-butyrolactone (alias 2-mercapto-4-butanolide), 2-mercapto-4- Methyl-4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butylothiolactone, 2-mercapto-4-butyrolactam, N-methoxy 2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mer Capto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-valerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valero Lactam, N- (2-methoxy) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam and 2-mercapto-6 -Hexanolactam, etc. are mentioned.
이들 머캅토기를 갖는 복소환 화합물은 광경화성 수지 조성물의 현상성을 손상하는 일이 없는 것으로부터 바람직하고, 구체적으로는 특히 머캅토벤조티아졸, 3-머캅토-4-메틸-4H-1,2,4-트리아졸, 5-메틸-1,3,4-티아디아졸-2-티올, 1-페닐-5-머캅토-1H-테트라졸이 바람직하다.Heterocyclic compounds having these mercapto groups are preferable since they do not impair developability of the photocurable resin composition, and specifically, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1, Preference is given to 2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole.
이들 연쇄 이동제는 단독 또는 2종 이상을 병용할 수 있다.These chain transfer agents may be used alone or in combination of two or more.
이러한 연쇄 이동제의 총량은 카르복실기 함유 수지 100 질량부에 대하여 5 질량부 이하가 되는 범위인 것이 바람직하다. 5 질량부를 초과하면 필요 이상의 첨가에 의해 감도가 향상되지 않을 뿐만 아니라, 이들과 에틸렌성 불포화기가 반응하게 되어, 현상성이 저하되는 경향이 있다.It is preferable that the total amount of such chain transfer agents becomes a range which will be 5 mass parts or less with respect to 100 mass parts of carboxyl group-containing resin. If it exceeds 5 parts by mass, not only the sensitivity will be improved by addition of more than necessary, but also these and ethylenically unsaturated groups will react, and developability tends to decrease.
본 실시 형태의 광경화성 수지 조성물에는 내열성을 부여하기 위해서 열경화성 수지를 가할 수 있다. 구체적으로는 예를 들면 다관능 에폭시 화합물, 다관능 옥세탄 화합물, 에피술피드 수지 등 분자 중에 2개 이상의 환상 에테르기 및/또는 환상 티오에테르기(이하, 환상 (티오)에테르기라고 기재함), 폴리이소시아네이트 화합물, 블록 이소시아네이트 화합물 등 1분자 내에 2개 이상의 이소시아네이트기, 또는 블록화 이소시아네이트기를 갖는 화합물, 멜라민 수지, 벤조구아나민 수지 등의 아민 수지와 그의 유도체, 비스말레이미드, 옥사진, 시클로카보네이트 화합물, 카르보디이미드 수지 등의 공지된 열경화성 수지를 들 수 있다.A thermosetting resin can be added to the photocurable resin composition of this embodiment in order to provide heat resistance. Specifically, for example, two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in a molecule such as a polyfunctional epoxy compound, a polyfunctional oxetane compound, and an episulfide resin , Amine resins such as polyisocyanate compounds, blocked isocyanate compounds, compounds having two or more isocyanate groups or blocked isocyanate groups, melamine resins, benzoguanamine resins, derivatives thereof, bismaleimide, oxazine, cyclocarbonate compounds, etc. And well-known thermosetting resins, such as carbodiimide resin, are mentioned.
특히 바람직한 것은, 분자 중에 2개 이상의 환상 (티오)에테르기를 갖는 열경화성 수지이다. 이러한 분자 중에 2개 이상의 환상 (티오)에테르기를 갖는 열경화성 수지는 분자 중에 3, 4 또는 5원환의 환상 에테르기, 또는 환상 티오에테르기중 어느 한쪽 또는 2종의 기를 2개 이상 갖는 화합물이고, 예를 들면 분자 내에 적어도 2개 이상의 에폭시기를 갖는 화합물, 즉 다관능 에폭시 화합물, 분자 내에 적어도 2개 이상의 옥세타닐기를 갖는 화합물, 즉 다관능 옥세탄 화합물, 분자 내에 2개 이상의 에피술피드기를 갖는 화합물, 즉 에피술피드 수지 등을 들 수 있다.Especially preferred is a thermosetting resin having two or more cyclic (thio) ether groups in the molecule. A thermosetting resin having two or more cyclic (thio) ether groups in such a molecule is a compound having at least two or three or more of three, four or five membered cyclic ether groups, or cyclic thioether groups in the molecule. For example, a compound having at least two or more epoxy groups in a molecule, that is, a polyfunctional epoxy compound, a compound having at least two or more oxetanyl groups in a molecule, that is, a polyfunctional oxetane compound, a compound having two or more episulfide groups in a molecule, That is, episulfide resin etc. are mentioned.
다관능 에폭시 화합물로서는, 구체적으로는 시판품으로서는 예를 들면 미쯔비시 가가꾸사 제조의 jER(등록상표) 828, jER834, jER1001, jER1004, DIC사 제조의 에피클론(등록상표) 840, 에피클론 850, 에피클론 1050, 에피클론 2055, 신닛까 에폭시 세이조우사 제조의 에포토토(등록상표) YD-011, YD-013, YD-127, YD-128, 다우 케미컬사 제조의 D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664, 헌츠맨 어드밴스드 머터리얼즈사 제조의 아랄다이트 6071, 아랄다이트 6084, 아랄다이트 GY250, 아랄다이트 GY260, 스미토모 가가꾸 고교사 제조의 스미에폭시(등록상표) ESA-011, ESA-014, ELA-115, ELA-128, 아사히 가세이 고교사 제조의 A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 등의 비스페놀 A형 에폭시 수지; 미쯔비시 가가꾸사 제조의 jERYL903, DIC사 제조의 에피클론 152, 에피클론 165, 신닛까 에폭시 세이조우사 제조의 에포토토 YDB-400, YDB-500, 다우 케미컬사 제조의 D.E.R.542, 바스프 재팬사 제조의 아랄다이트 8011, 스미토모 가가꾸 고교사 제조의 스미에폭시ESB-400, ESB-700, 아사히 가세이 고교사 제조의 A.E.R.711, A.E.R.714 등의 브롬화 에폭시 수지; 미쯔비시 가가꾸사 제조의 jER152, jER154, 다우 케미컬사 제조의 D.E.N.431, D.E.N.438, DIC사 제조의 에피클론 N-730, 에피클론 N-770, 에피클론 N-865, 신닛까 에폭시 세이조우사 제조의 에포토토 YDCN-701, YDCN-704, 바스프 재팬사 제조의 아랄다이트 ECN1235, 아랄다이트 ECN1273, 아랄다이트 ECN1299, 아랄다이트 XPY307, 닛본 가야꾸사 제조의 EPPN(등록상표)-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, 스미토모 가가꾸 고교사 제조의 스미에폭시 ESCN-195 X, ESCN-220, 아사히 가세이 고교사 제조의 A.E.R.ECN-235, ECN-299 등의 노볼락형 에폭시 수지; DIC사 제조의 에피클론 830, 미쯔비시 가가꾸사 제조의 jER807, 신닛까 에폭시 세이조우사 제조의 에포토토 YDF-170, YDF-175, YDF-2004, 바스프 재팬사 제조의 아랄다이트 XPY306 등의 비스페놀 F형 에폭시 수지; 신닛까 에폭시 세이조우사 제조의 에포토토 ST-2004, ST-2007, ST-3000 등의 수소 첨가 비스페놀 A형 에폭시 수지; 미쯔비시 가가꾸사 제조의 jER604, 신닛까 에폭시 세이조우사 제조의 에포토토 YH-434, 바스프 재팬사 제조의 아랄다이트 MY720, 스미토모 가가꾸 고교사 제조의 스미에폭시 ELM-120 등의 글리시딜아민형 에폭시 수지; 바스프 재팬사 제조의 아랄다이트 CY-350 등의 히단토인형 에폭시 수지; 다이셀 가가꾸 고교사 제조의 셀록사이드(등록상표) 2021, 바스프 재팬사 제조의 아랄다이트 CY175, CY179 등의 지환식 에폭시 수지; 미쯔비시 가가꾸사 제조의 YL-933, 다우 케미컬사 제조의 T.E.N., EPPN-501, EPPN-502 등의 트리히드록시페닐 메탄형 에폭시 수지; 미쯔비시 가가꾸사 제조의 YL-6056, YX-4000, YL-6121 등의 비크실레놀형 또는 비페놀형 에폭시 수지 또는 이들의 혼합물; 닛본 가야꾸사 제조의 EBPS-200, 아데카사 제조의 EPX-30, DIC사 제조의 EXA-1514 등의 비스페놀 S형 에폭시 수지; 미쯔비시 가가꾸사 제조의 jER157S 등의 비스페놀 A 노볼락형 에폭시 수지; 미쯔비시 가가꾸사 제조의 jERYL-931, 바스프 재팬사 제조의 아랄다이트 163 등의 테트라페닐올에탄형 에폭시 수지; 바스프 재팬사 제조의 아랄다이트 PT810, 닛산 가가꾸 고교사 제조의 TEPIC(등록상표) 등의 복소환식 에폭시 수지; 니찌유사 제조의 브렘머(등록상표) DGT 등의 디글리시딜프탈레이트 수지; 신닛까 에폭시 세이조우사 제조의 ZX-1063 등의 테트라글리시딜크실레노일에탄 수지; 신닛테쯔 가가꾸사 제조의 ESN-190, ESN-360, DIC사 제조의 HP-4032, EXA-4750, EXA-4700 등의 나프탈렌기 함유 에폭시 수지; DIC사 제조의 HP-7200, HP-7200H 등의 디시클로펜타디엔 골격을 갖는 에폭시 수지; 니찌유사 제조의 CP-50S, CP-50M 등의 글리시딜메타크릴레이트 공중합계 에폭시 수지; 또한 시클로헥실말레이미드와 글리시딜메타크릴레이트의 공중합 에폭시 수지; 다이셀 가가꾸 고교 제조 PB-3600 등의 에폭시 변성의 폴리부타디엔고무 유도체, 신닛까 에폭시 세이조우사 제조의 YR-102, YR-450 등의 CTBN 변성 에폭시 수지 등을 들 수 있다.As a polyfunctional epoxy compound, specifically, as a commercial item, jER (trademark) 828, jER834, jER1001, jER1004 by Mitsubishi Chemical Corporation, Epiclone (trademark) 840, Epiclone 850, and Epi make Clone 1050, Epiclone 2055, Eptoto (registered trademark) YD-011, YD-013, YD-127, YD-128, DER317, DER331, DER made by Epoxy Seiko Co., Ltd. 661, DER664, Araldite 6071 made by Huntsman Advanced Materials, Araldite 6084, Araldite GY250, Araldite GY260, Sumitomo (registered trademark) ESA-011 made by Sumitomo Kagaku Kogyo Co., Ltd. Bisphenol A type epoxy resins such as AER330, AER331, AER661, and AER664 manufactured by ESA-014, ELA-115, ELA-128, and Asahi Kasei Kogyo Co., Ltd .; JERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclone 152 manufactured by DIC Corporation, Epiclone 165, Efototo YDB-400, YDB-500 manufactured by Shinnika Epoxy Seizou Corporation, DER542 manufactured by Dow Chemical, BASF Japan Brominated epoxy resins such as Araldite 8011, Sumitomo Chemical Co., Ltd., Sumerepoxy ESB-400, ESB-700, and Asahi Kasei Kogyo AER711, AER714; Mitsubishi Chemical Corporation jER152, jER154, Dow Chemical Co., Ltd. DEN431, DEN438, DIC Co., Ltd. Epiclone N-730, Epiclone N-770, Epiclone N-865, Shin-Nika Epoxy Seizo Co., Ltd. Efototo YDCN-701, YDCN-704, Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 by BASF Japan, EPPN (registered trademark) -201, manufactured by Nippon Kayaku Co., Ltd. EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Kagaku Kogyo Co., Ltd. Sumiepoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo AERECN-235, ECN-299, etc. Novolac type epoxy resins; Epiclon 830, manufactured by DIC Corporation, jER807, manufactured by Mitsubishi Chemical Corporation, Efototo YDF-170, YDF-175, YDF-2004, manufactured by BASF Japan, and Araldite XPY306, manufactured by BASF Japan. Bisphenol F type epoxy resin; Hydrogenated bisphenol A type epoxy resins such as Efototo ST-2004, ST-2007, ST-3000 manufactured by Shinnika Epoxy Seijo Corporation; Glycidyl such as jER604 manufactured by Mitsubishi Chemical Corporation, Efototo YH-434 manufactured by Shintika Epoxy Seizo Corporation, Araldite MY720 manufactured by BASF Japan, Sumiepoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. Amine type epoxy resins; Hydantoin type epoxy resins, such as Araldite CY-350 by BASF Japan company; Alicyclic epoxy resins such as Celoxide (registered trademark) 2021 manufactured by Daicel Chemical Industries, Ltd., Araldite CY175 manufactured by BASF Japan, and CY179; Trihydroxyphenyl methane type epoxy resins such as YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501 and EPPN-502 manufactured by Dow Chemical Corporation; Bixylenol type or biphenol type epoxy resins such as YL-6056, YX-4000, YL-6121 manufactured by Mitsubishi Chemical Corporation, or mixtures thereof; Bisphenol S type epoxy resins, such as EBPS-200 by Nippon Kayaku Co., Ltd., EPX-30 by Adeka Co., and EXA-1514 by DIC Co., Ltd .; Bisphenol A novolak-type epoxy resins, such as the jER157S by Mitsubishi Chemical Corporation; Tetraphenylolethane type epoxy resins such as jERYL-931 manufactured by Mitsubishi Chemical Corporation and Araldite 163 manufactured by BASF Japan; Heterocyclic epoxy resins such as Araldite PT810 manufactured by BASF Japan, TEPIC (registered trademark) manufactured by Nissan Chemical Industries, Ltd .; Diglycidyl phthalate resins such as Bremmer (registered trademark) DGT manufactured by Nichi Oil Company; Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Shinnika Epoxy Seijo Co .; ESN-190, ESN-360 manufactured by Shinnittsu Chemical Co., Ltd., HP-4032, EXA-4750 and EXA-4700 manufactured by DIC Corporation; An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; Glycidyl methacrylate copolymer-based epoxy resins such as CP-50S and CP-50M manufactured by Nichi Oil Company; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives, such as Daicel Chemical Industries, Ltd. PB-3600, CTBN modified epoxy resins, such as YR-102 and YR-450, manufactured by Shin-Naka Epoxy Seizo Co., etc. are mentioned.
이들 다관능 에폭시 화합물은 단독으로 또는 2종 이상을 조합하여 사용할 수 있다. 이들 중에서도 특히 노볼락형 에폭시 수지, 복소환식 에폭시 수지, 비스페놀 A형 에폭시 수지 또는 이들의 혼합물이 바람직하다.These polyfunctional epoxy compounds can be used individually or in combination of 2 or more types. Of these, novolak type epoxy resins, heterocyclic epoxy resins, bisphenol A type epoxy resins, and mixtures thereof are particularly preferable.
다관능 옥세탄 화합물로서는, 구체적으로는 예를 들면 비스[(3-메틸-3-옥세타닐메톡시)메틸]에테르, 비스[(3-에틸-3-옥세타닐메톡시)메틸]에테르, 1,4-비스[(3-메틸-3-옥세타닐메톡시)메틸]벤젠, 1,4-비스[(3-에틸-3-옥세타닐메톡시)메틸]벤젠, (3-메틸-3-옥세타닐)메틸아크릴레이트, (3-에틸-3-옥세타닐)메틸아크릴레이트, (3-메틸-3-옥세타닐)메틸메타크릴레이트, (3-에틸-3-옥세타닐)메틸메타크릴레이트나 이들의 올리고머 또는 공중합체 등의 다관능 옥세탄류 외에, 옥세탄 알코올과 노볼락 수지, 폴리(p-히드록시스티렌), 카르도형 비스페놀류, 칼릭스아렌류, 칼릭스레조르신아렌류 또는 실세스퀴옥산 등의 수산기를 갖는 수지와의 에테르화물 등을 들 수 있다. 기타, 옥세탄환을 갖는 불포화 단량체와 알킬(메트)아크릴레이트와의 공중합체 등도 들 수 있다.Specific examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1 , 4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3- Oxetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl methacrylate and oligomers or copolymers thereof, oxetane alcohols, novolak resins, poly (p-hydroxystyrene), cardo bisphenols, calix arenes and calyx rezos The etherified substance with resin which has hydroxyl groups, such as a leucine arene or silsesquioxane, etc. are mentioned. Other examples include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.
에피술피드 수지로서는, 구체적으로는 예를 들면 미쯔비시 가가꾸사 제조의 YL7000 등의 비스페놀 A형 에피술피드 수지 등을 들 수 있다. 또한, 동일한 합성 방법을 이용하여 노볼락형 에폭시 수지의 에폭시기의 산소 원자를 황 원자로 대체한 에피술피드 수지 등도 사용할 수 있다.Specific examples of the episulfide resin include bisphenol A episulfide resins such as YL7000 manufactured by Mitsubishi Chemical Corporation. An episulfide resin in which an oxygen atom of the epoxy group of the novolac epoxy resin is replaced with a sulfur atom using the same synthetic method can also be used.
이러한 분자 중에 2개 이상의 환상 (티오)에테르기를 갖는 열경화성 수지의 배합량은 카르복실기 함유 수지의 카르복실기 1 당량에 대하여 0.6 내지 2.5 당량인 것이 바람직하다. 0.6 당량 미만인 경우, 솔더 레지스트막에 카르복실기가 남아, 내열성, 내알칼리성, 전기 절연성 등이 저하된다. 한편, 2.5 당량을 초과하는 경우, 저분자량의 환상 (티오)에테르기가 건조 도막에 잔존함으로써 도막의 강도 등이 저하된다. 보다 바람직하게는 0.8 내지 2.0 당량이다.It is preferable that the compounding quantity of the thermosetting resin which has two or more cyclic (thio) ether group in such a molecule | numerator is 0.6-2.5 equivalent with respect to 1 equivalent of carboxyl group of carboxyl group-containing resin. When less than 0.6 equivalent, a carboxyl group remains in a soldering resist film, and heat resistance, alkali resistance, electrical insulation, etc. fall. On the other hand, when it exceeds 2.5 equivalents, the strength and the like of the coating film deteriorate because a low molecular weight cyclic (thio) ether group remains in the dried coating film. More preferably 0.8 to 2.0 equivalents.
또한, 1분자 내에 2개 이상의 이소시아네이트기, 또는 블록화 이소시아네이트기를 갖는 화합물로서는 1분자 내에 2개 이상의 이소시아네이트기를 갖는 화합물, 즉 폴리이소시아네이트 화합물, 또는 1분자 내에 2개 이상의 블록화 이소시아네이트기를 갖는 화합물, 즉 블록 이소시아네이트 화합물 등을 들 수 있다.As a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule, a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or a compound having two or more blocked isocyanate groups in one molecule, that is, a blocked isocyanate group Compounds and the like.
폴리이소시아네이트 화합물로서는, 예를 들면 방향족 폴리이소시아네이트, 지방족 폴리이소시아네이트 또는 지환식 폴리이소시아네이트가 이용된다.As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.
방향족 폴리이소시아네이트로서는, 구체적으로는 예를 들면 4,4'-디페닐메탄디이소시아네이트, 2,4-톨릴렌디이소시아네이트, 2,6-톨릴렌디이소시아네이트, 나프탈렌-1,5-디이소시아네이트, o-크실릴렌디이소시아네이트, m-크실릴렌디이소시아네이트 및 2,4-톨릴렌 이량체를 들 수 있다.Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate and o-chloro Silylene diisocyanate, m-xylylene diisocyanate and 2,4-tolylene dimer are mentioned.
지방족 폴리이소시아네이트로서는, 구체적으로는 예를 들면 테트라메틸렌디이소시아네이트, 헥사메틸렌디이소시아네이트, 메틸렌디이소시아네이트, 트리메틸헥사메틸렌디이소시아네이트, 4,4-메틸렌비스(시클로헥실이소시아네이트) 및 이소포론디이소시아네이트를 들 수 있다.Specific examples of the aliphatic polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. have.
지환식 폴리이소시아네이트로서는, 구체적으로는 예를 들면 비시클로헵탄트리이소시아네이트를 들 수 있다.Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate.
1분자 내에 2개 이상의 블록화 이소시아네이트기를 갖는 블록 이소시아네이트 화합물로서는 이소시아네이트 화합물과 이소시아네이트 블록제와의 부가 반응 생성물이 이용된다. 블록 이소시아네이트 화합물에 포함되는 블록화 이소시아네이트기는 이소시아네이트기가 블록제와의 반응에 의해 보호되어 일시적으로 불활성화된 기이다. 그리고, 이러한 블록화 이소시아네이트기가 소정 온도로 가열된 때에, 그의 블록제가 해리하여 이소시아네이트기가 생성된다.As a block isocyanate compound which has two or more blocked isocyanate groups in 1 molecule, the addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. The blocked isocyanate group contained in the block isocyanate compound is a group in which the isocyanate group is protected by a reaction with the blocking agent and is temporarily inactivated. When the blocked isocyanate group is heated to a predetermined temperature, the blocking agent dissociates to form an isocyanate group.
이소시아네이트 블록제와 반응할 수 있는 이소시아네이트 화합물로서는 이소시아누레이트형, 뷰렛형, 어덕트형 등을 들 수 있다. 예를 들면, 방향족 폴리이소시아네이트, 지방족 폴리이소시아네이트 또는 지환식 폴리이소시아네이트가 이용된다.Isocyanurate type, a biuret type, an adduct type etc. are mentioned as an isocyanate compound which can react with an isocyanate blocking agent. For example, aromatic polyisocyanates, aliphatic polyisocyanates or alicyclic polyisocyanates are used.
방향족 폴리이소시아네이트로서는, 구체적으로는 예를 들면 4,4'-디페닐메탄디이소시아네이트, 2,4-톨릴렌디이소시아네이트, 2,6-톨릴렌디이소시아네이트, 나프탈렌-1,5-디이소시아네이트, o-크실릴렌디이소시아네이트, m-크실릴렌디이소시아네이트 및 2,4-톨릴렌 이량체를 들 수 있다.Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate and o-chloro Silylene diisocyanate, m-xylylene diisocyanate and 2,4-tolylene dimer are mentioned.
지방족 폴리이소시아네이트로서는, 구체적으로는 예를 들면 테트라메틸렌디이소시아네이트, 헥사메틸렌디이소시아네이트, 메틸렌디이소시아네이트, 트리메틸헥사메틸렌디이소시아네이트, 4,4-메틸렌비스(시클로헥실이소시아네이트) 및 이소포론디이소시아네이트를 들 수 있다.Specific examples of the aliphatic polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. have.
지환식 폴리이소시아네이트로서는, 구체적으로는 비시클로헵탄트리이소시아네이트를 들 수 있다.Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate.
이소시아네이트 블록제로서는, 구체적으로는 예를 들면 페놀, 크레졸, 크실레놀, 클로로페놀 및 에틸페놀 등의 페놀계 블록제; ε-카프로락탐, δ-발레로락탐, γ-부티로락탐 및 β-프로피오락탐 등의 락탐계 블록제; 아세토아세트산에틸 및 아세틸아세톤 등의 활성 메틸렌계 블록제; 메탄올, 에탄올, 프로판올, 부탄올, 아밀 알코올, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노부틸에테르, 디에틸렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르, 벤질에테르, 글리콜산메틸, 글리콜산부틸, 디아세톤알코올, 락트산메틸 및 락트산에틸 등의 알코올계 블록제; 포름알데히독심, 아세토알독심, 아세톡심, 메틸에틸케톡심, 디아세틸모노옥심, 시클로헥산옥심 등의 옥심계 블록제; 부틸머캅탄, 헥실머캅탄, t-부틸머캅탄, 티오페놀, 메틸티오페놀, 에틸티오페놀 등의 머캅탄계 블록제; 아세트산아미드, 벤즈아미드 등의 산아미드계 블록제; 숙신산이미드 및 말레산이미드 등의 이미드계 블록제; 크실리딘, 아닐린, 부틸아민, 디부틸아민 등의 아민계 블록제; 이미다졸, 2-에틸이미다졸 등의 이미다졸계 블록제; 메틸렌이민 및 프로필렌이민 등의 이민계 블록제 등을 들 수 있다.As an isocyanate blocking agent, For example, Phenol blocking agents, such as a phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam-based blocking agents such as? -caprolactam,? -valerolactam,? -butyrolactam and? -propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; Methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, glycol Alcohol blocking agents such as butyl acid, diacetone alcohol, methyl lactate and ethyl lactate; Oxime-based blocking agents such as formaldehyde scavengers, acetal aldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol and ethyl thiophenol; Acid amide block agents such as acetic amide and benzamide; Imide block agents such as succinic acid imide and maleic acid imide; Amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; Imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine blockers such as methylene imine and propylene imine, and the like.
블록 이소시아네이트 화합물은 시판되고 있는 것이어도 되고, 예를 들면 스미토모 바이엘 우레탄사 제조의 스미듀르(등록상표) BL-3175, BL-4165, BL-1100, BL-1265, 데스모듀르(등록상표) TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, 데스모템(DESMOTHERM; 등록상표) 2170, 데스모템 2265, 닛본 폴리우레탄 고교사 제조 코로네이트(등록상표) 2512, 코로네이트 2513, 코로네이트 2520, 미쓰이다케다 케미컬사 제조의 B-830, B-815, B-846, B-870, B-874, B-882, 아사히 가세이 케미컬즈사 제조의 TPA-B80E, 17B-60PX, E402-B80T 등을 들 수 있다. 또한, 스미듀르 BL-3175, BL-4265는 블록제로서 메틸에틸옥심을 이용하여 얻어지는 것이다.A block isocyanate compound may be commercially available, for example, Sumidur (R) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (TM) TPLS by Sumitomo Bayer Urethane Co., Ltd. -2957, TPLS-2062, TPLS-2078, TPLS-2117, Des Motem (DESMOTHERM; 2170), Des Motem 2265, Nippon Polyurethane Co., Ltd. Coronate 2512, Coronate 2513, Coronate 2520 , B-830, B-815, B-846, B-870, B-874, B-882, TPA-B80E, 17B-60PX, E402-B80T manufactured by Asahi Kasei Chemicals, Inc. Can be mentioned. Further, SMILDIR BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a block agent.
이들 1분자 내에 2개 이상의 이소시아네이트기, 또는 블록화 이소시아네이트기를 갖는 화합물은 1종을 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The compound which has two or more isocyanate groups or blocked isocyanate groups in these 1 molecule can be used individually by 1 type or in combination of 2 or more types.
이러한 1분자 내에 2개 이상의 이소시아네이트기, 또는 블록화 이소시아네이트기를 갖는 화합물의 배합량은 카르복실기 함유 수지 100 질량부에 대하여 1 내지 100 질량부인 것이 바람직하다. 1 질량부 미만의 경우, 충분한 도막의 강인성이 얻어지지 않고, 한편 100 질량부를 초과한 경우, 보존 안정성이 저하된다. 보다 바람직하게는 2 내지 70 질량부이다.It is preferable that the compounding quantity of the compound which has two or more isocyanate groups or blocked isocyanate groups in such 1 molecule is 1-100 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When it is less than 1 mass part, sufficient toughness of a coating film is not obtained, and when it exceeds 100 mass parts, storage stability falls. More preferably 2 to 70 parts by mass.
또한, 열경화성 수지로서, 멜라민 수지나 벤조구아나민 수지 등의 아민 수지 및 그의 유도체 등을 들 수 있다. 구체적으로는 예를 들면 메틸올멜라민 화합물, 메틸올벤조구아나민 화합물, 메틸올글리콜우릴 화합물 및 메틸올요소 화합물 등을 들 수 있다.Moreover, amine resins, such as melamine resin and benzoguanamine resin, its derivative (s) etc. are mentioned as a thermosetting resin. Specifically, a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, a methylol urea compound, etc. are mentioned, for example.
또한, 이들 메틸올기를 알콕시메틸기로 변환함으로써 얻어지는 알콕시메틸화멜라민 화합물, 알콕시메틸화벤조구아나민 화합물, 알콕시메틸화글리콜우릴 화합물 및 알콕시메틸화요소 화합물을 사용할 수 있다. 이 때, 알콕시메틸기의 종류에 대해서는 특별히 한정되는 것은 아니고, 예를 들면 메톡시메틸기, 에톡시메틸기, 프로폭시메틸기, 부톡시메틸기 등으로 할 수 있다. 특히 인체나 환경 친화적인 포르말린 농도가 0.2% 이하인 것이 바람직하다.Moreover, the alkoxy methylation melamine compound, the alkoxy methylation benzoguanamine compound, the alkoxy methylation glycoluril compound, and the alkoxy methylation element compound which are obtained by converting these methylol groups by the alkoxy methyl group can be used. At this time, it does not specifically limit about the kind of alkoxy methyl group, For example, it can be set as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group. In particular, it is preferable that the concentration of formalin that is human or environmentally friendly is 0.2% or less.
이들 시판품으로서는, 구체적으로는 예를 들면 미쓰이 사이아나미드사 제조의 사이멜(등록상표) 300, 동301, 동303, 동370, 동325, 동327, 동701, 동266, 동267, 동238, 동1141, 동272, 동202, 동1156, 동1158, 동1123, 동1170, 동1174, 동 UFR65, 동300, 산와 케미컬사 제조의 니칼락(등록상표) Mx-750, 동 Mx-032, 동 Mx-270, 동 Mx-280, 동 Mx-290, 동 Mx-706, 동 Mx-708, 동 Mx-40, 동 Mx-31, 동 Ms-11, 동 Mw-30, 동 Mw-30HM, 동 Mw-390, 동 Mw-100LM, 동 Mw-750LM 등을 들 수 있다.As these commercial items, Cymel (registered trademark) 300, copper 301, copper 303, copper 370, copper 325, copper 327, copper 701, copper 266, copper 267, copper manufactured by Mitsui Cyanamide, for example. 238, copper 1141, copper 272, copper 202, copper 1156, copper 1158, copper 1123, copper 1170, copper 1174, copper UFR65, copper 300, Nikalak (registered trademark) Mx-750, copper Mx- 032, Mx-270, Mx-280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw- 30HM, copper Mw-390, copper Mw-100LM, copper Mw-750LM, etc. are mentioned.
이들 열경화성 수지는 단독 또는 2종 이상을 병용할 수 있다.These thermosetting resins can be used individually or in combination of 2 or more types.
이러한 아민 수지 및 그의 유도체의 배합량은 카르복실기 함유 수지 100 질량부에 대하여 1 내지 100 질량부인 것이 바람직하다. 1 질량부 미만의 경우, 충분한 도막의 강인성이 얻어지지 않고, 한편 100 질량부를 초과한 경우, 보존 안정성이 저하된다. 보다 바람직하게는 2 내지 70 질량부이다.It is preferable that the compounding quantity of such an amine resin and its derivatives is 1-100 mass parts with respect to 100 mass parts of carboxyl group-containing resin. When it is less than 1 mass part, sufficient toughness of a coating film is not obtained, and when it exceeds 100 mass parts, storage stability falls. More preferably 2 to 70 parts by mass.
분자 중에 2개 이상의 환상 (티오)에테르기를 갖는 열경화성 수지를 사용하는 경우, 열경화 촉매를 함유하는 것이 바람직하다. 그와 같은 열경화 촉매로서는, 구체적으로는 예를 들면 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸, 2-에틸-4-메틸이미다졸, 2-페닐이미다졸, 4-페닐이미다졸, 1-시아노에틸-2-페닐이미다졸, 1-(2-시아노에틸)-2-에틸-4-메틸이미다졸 등의 이미다졸 유도체; 디시안디아미드, 벤질디메틸아민, 4-(디메틸아미노)-N,N-디메틸벤질아민, 4-메톡시-N,N-디메틸벤질아민, 4-메틸-N,N-디메틸벤질아민 등의 아민 화합물, 아디프산디히드라지드, 세박산디히드라지드 등의 히드라진 화합물; 트리페닐포스핀 등의 인 화합물 등을 들 수 있다.When using the thermosetting resin which has a 2 or more cyclic (thio) ether group in a molecule | numerator, it is preferable to contain a thermosetting catalyst. Specific examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4 Imidazole derivatives such as -phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine.
또한, 시판되고 있는 것으로서는, 구체적으로는 예를 들면 이미다졸계 화합물로서, 시코쿠 가세이 고교사 제조의 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ, 산 아프로사 제조의 U-CAT(등록상표) 3503N, U-CAT3502T(모두 디메틸아민의 블록 이소시아네이트 화합물의 상품명), DBU, DBN, U-CATSA102, U-CAT5002(모두 이환식 아미딘 화합물 및 그의 염) 등을 들 수 있다. 특히, 이들에 한정되는 것은 아니고, 에폭시 수지나 옥세탄 화합물의 열경화 촉매, 또는 에폭시기 및/또는 옥세타닐기와 카르복실기의 반응을 촉진하는 열경화 촉매이면 되고, 단독 또는 2종 이상을 병용할 수 있다.As commercially available products, specifically, for example, an imidazole compound, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ manufactured by Shikoku Kasei Kogyo Co., Ltd. Trademark) 3503N, U-CAT3502T (all are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all bicyclic amidine compounds and salts thereof) and the like. In particular, it is not limited to these, What is necessary is just the thermosetting catalyst of an epoxy resin or an oxetane compound, or the thermosetting catalyst which promotes reaction of an epoxy group and / or an oxetanyl group, and a carboxyl group, and can use together single or 2 types or more. have.
또한, 밀착성 부여제로서도 기능하는 구아나민, 아세토구아나민, 벤조구아나민, 멜라민, 2,4-디아미노-6-메타크릴로일옥시에틸-S-트리아진, 2-비닐-2,4-디아미노-S-트리아진, 2-비닐-4, 6-디아미노-S-트리아진·이소시아누르산 부가물, 2,4-디아미노-6-메타크릴로일옥시에틸-S-트리아진·이소시아누르산 부가물 등의 S-트리아진 유도체를 이용할 수도 있다. 이들을 열경화 촉매와 병용하는 것이 보다 바람직하다.In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine and 2-vinyl-2,4-, which also function as an adhesion imparting agent Diamino-S-triazine, 2-vinyl-4, 6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-tri S-triazine derivatives, such as an azine and isocyanuric acid adduct, can also be used. It is more preferable to use these together with a thermosetting catalyst.
이들 열경화 촉매의 배합량은 통상의 양적 비율로 충분하고, 예를 들면 카르복실기 함유 수지 또는 분자 중에 2개 이상의 환상 (티오)에테르기를 갖는 열경화성 수지 100 질량부에 대하여 바람직하게는 0.1 내지 20 질량부, 보다 바람직하게는 0.5 내지 15.0 질량부이다.The compounding quantity of these thermosetting catalysts is sufficient in a normal quantitative ratio, For example, 0.1-20 mass parts with respect to 100 mass parts of thermosetting resins which have two or more cyclic (thio) ether groups in a carboxyl group-containing resin or molecule | numerator, More preferably, it is 0.5-15.0 mass parts.
본 실시 형태의 광경화성 수지 조성물에는 층간의 밀착성, 또는 감광성 수지층과 기재와의 밀착성을 향상시키기 위해서 밀착 촉진제를 사용할 수 있다. 구체적으로는 예를 들면 벤즈이미다졸, 벤즈옥사졸, 벤즈티아졸, 2-머캅토벤즈이미다졸, 2-머캅토벤즈옥사졸, 2-머캅토벤즈티아졸, 3-모르폴리노메틸-1-페닐-트리아졸-2-티온, 5-아미노-3-모르폴리노메틸-티아졸-2-티온, 2-머캅토-5-메틸티오-티아디아졸, 트리아졸, 테트라졸, 벤조트리아졸, 카르복시벤조트리아졸, 아미노기 함유 벤조트리아졸, 실란 커플링제 등을 들 수 있다.An adhesion promoter can be used for the photocurable resin composition of this embodiment in order to improve adhesiveness between layers or adhesiveness of the photosensitive resin layer and a base material. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1, for example -Phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotria Sol, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.
또한, 본 실시 형태의 광경화성 수지 조성물에는 지촉 건조성의 개선, 취급성의 개선 등을 목적으로 결합제 중합체를 사용할 수 있다. 결합제 중합체로서는, 예를 들면 폴리에스테르계 중합체, 폴리우레탄계 중합체, 폴리에스테르우레탄계 중합체, 폴리아미드계 중합체, 폴리에스테르아미드계 중합체, 아크릴계 중합체, 셀룰로오스계 중합체, 폴리락트산계 중합체, 페녹시계 중합체 등을 들 수 있다. 이들 결합제 중합체는 단독으로 또는 2종 이상의 혼합물로서 사용할 수 있다.In addition, a binder polymer can be used for the photocurable resin composition of this embodiment for the purpose of improving a touch-drying property, an improvement of handleability, etc. Examples of the binder polymer include polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyesteramide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, and phenoxy clock polymers. Can be. These binder polymers can be used alone or as a mixture of two or more thereof.
또한, 본 실시 형태의 광경화성 수지 조성물은 유연성의 부여, 경화물의 취약함을 개선하는 것 등을 목적으로 엘라스토머를 사용할 수 있다. 엘라스토머로서는 예를 들면 폴리에스테르계 엘라스토머, 폴리우레탄계 엘라스토머, 폴리에스테르우레탄계 엘라스토머, 폴리아미드계 엘라스토머, 폴리에스테르아미드계 엘라스토머, 아크릴계 엘라스토머, 올레핀계 엘라스토머를 들 수 있다. 또한, 여러가지의 골격을 갖는 에폭시 수지의 일부 또는 전부의 에폭시기를 양쪽 말단 카르복실산 변성형 부타디엔-아크릴로니트릴고무로 변성한 엘라스토머 등도 사용할 수 있다. 또한, 에폭시 함유 폴리부타디엔계 엘라스토머, 아크릴 함유 폴리부타디엔계 엘라스토머, 수산기 함유 폴리부타디엔계 엘라스토머, 수산기 함유 이소프렌계 엘라스토머 등도 사용할 수 있다. 이들 엘라스토머는 단독으로 또는 2종 이상의 혼합물로서 사용할 수 있다.In addition, the photocurable resin composition of this embodiment can use an elastomer for the purpose of providing flexibility, improving the fragility of hardened | cured material, etc. Examples of the elastomer include a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyester amide elastomer, an acrylic elastomer and an olefin elastomer. Moreover, the elastomer etc. which modified | denatured some or all the epoxy groups of the epoxy resin which has various skeletons with both terminal carboxylic acid modified butadiene- acrylonitrile rubber can also be used. The epoxy-containing polybutadiene elastomer, the acrylic-containing polybutadiene elastomer, the hydroxyl group-containing polybutadiene elastomer, and the hydroxyl group-containing isoprene elastomer may also be used. These elastomers can be used alone or as a mixture of two or more thereof.
또한, 본 실시 형태의 광경화성 수지 조성물은 착색제를 배합할 수 있다. 착색제로서는 청색, 녹색, 황색, 적색 등의 공지된 착색제를 사용할 수 있고, 안료, 염료, 색소 중의 어느 것이어도 된다. 단, 환경 부하 감소 및 인체에의 영향의 관점에서 할로겐을 함유하지 않는 것이 바람직하다. 구체적으로는 이하와 같은 컬러 인덱스(C.I.; The Society of Dyers and Colourists 발행) 번호가 첨부되어 있는 것을 들 수 있다In addition, the photocurable resin composition of this embodiment can mix | blend a coloring agent. As a coloring agent, well-known coloring agents, such as blue, green, yellow, and red, can be used, and any of a pigment, dye, and a pigment may be used. However, it is preferable not to contain a halogen from a viewpoint of environmental load reduction and an influence on a human body. Specifically, the following color index (C.I .; issued by The Society of Dyers and Colorists) numbers is attached.
청색 착색제로서는 프탈로시아닌계, 안트라퀴논계 등이 이용된다. 안료계로서는, 예를 들면 피그먼트 블루 15, 피그먼트 블루 15:1, 피그먼트 블루 15:2, 피그먼트 블루 15:3, 피그먼트 블루 15:4, 피그먼트 블루 15:6, 피그먼트 블루 16, 피그먼트 블루 60을 들 수 있다.Phthalocyanine series, anthraquinone series, etc. are used as a blue coloring agent. As a pigment system, for example, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, pigment blue 60 is mentioned.
염료계로서는, 예를 들면 솔벤트 블루 35, 솔벤트 블루 63, 솔벤트 블루 68, 솔벤트 블루 70, 솔벤트 블루 83, 솔벤트 블루 87, 솔벤트 블루 94, 솔벤트 블루 97, 솔벤트 블루 122, 솔벤트 블루 136, 솔벤트 블루 67, 솔벤트 블루 70 등을 들 수 있다. 이들 이외에도, 금속 치환 또는 비치환된 프탈로시아닌 화합물도 사용할 수 있다.As the dye system, for example, solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 122, solvent blue 136, solvent blue 67 , Solvent blue 70, and the like. In addition to these, metal substituted or unsubstituted phthalocyanine compounds may also be used.
녹색 착색제로서는 마찬가지로 프탈로시아닌계, 안트라퀴논계나, 페릴렌계 등이 이용된다. 예를 들면, 피그먼트 그린 7, 피그먼트 그린 36, 솔벤트 그린 3, 솔벤트 그린 5, 솔벤트 그린 20, 솔벤트 그린 28 등을 들 수 있다. 이들 이외에도, 금속 치환 또는 비치환된 프탈로시아닌 화합물도 사용할 수 있다.As the green colorant, phthalocyanine series, anthraquinone series, perylene series and the like are used. For example, pigment green 7, pigment green 36, solvent green 3, solvent green 5, solvent green 20, solvent green 28, etc. are mentioned. In addition to these, metal substituted or unsubstituted phthalocyanine compounds may also be used.
황색 착색제로서는 모노아조계, 디스아조계, 축합 아조계, 벤즈이미다졸론계, 이소인돌리논계, 안트라퀴논계 등이 이용된다. 구체적으로는 이하의 것을 들 수 있다.As the yellow colorant, monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone and the like are used. Specifically, the following are mentioned.
모노아조계: 피그먼트 옐로우 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183Monoazo system: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111 , 116, 167, 168, 169, 182, 183
디스아조계: 피그먼트 옐로우 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198Disazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198
축합 아조계: 피그먼트 옐로우 93, 피그먼트 옐로우 94, 피그먼트 옐로우 95, 피그먼트 옐로우 128, 피그먼트 옐로우 155, 피그먼트 옐로우 166, 피그먼트 옐로우 180Condensation Azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180
벤즈이미다졸론계: 피그먼트 옐로우 120, 피그먼트 옐로우 151, 피그먼트 옐로우 154, 피그먼트 옐로우 156, 피그먼트 옐로우 175, 피그먼트 옐로우 18Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 18
이소인돌리논계: 피그먼트 옐로우 110, 피그먼트 옐로우 109, 피그먼트 옐로우 139, 피그먼트 옐로우 179, 피그먼트 옐로우 185Isoindolinone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185
안트라퀴논계: 솔벤트 옐로우 163, 피그먼트 옐로우 24, 피그먼트 옐로우 108, 피그먼트 옐로우 193, 피그먼트 옐로우 147, 피그먼트 옐로우 199, 피그먼트 옐로우 202Anthraquinone series: solvent yellow 163, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, pigment yellow 199, pigment yellow 202
적색 착색제로서는 모노아조계, 디스아조계, 모노아조레이크계, 벤즈이미다졸론계, 페릴렌계, 디케토피롤로피롤계, 축합 아조계, 안트라퀴논계, 퀴나크리돈계 등을 사용할 수 있다. 구체적으로는 이하의 것을 들 수 있다.As a red coloring agent, a monoazo system, a disazo system, a monoazo lake system, a benzimidazolone system, a perylene system, a diketopyrrolopyrrole system, a condensation azo system, an anthraquinone system, a quinacridone system, etc. can be used. Specifically, the following are mentioned.
모노아조계: 피그먼트 레드 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269Monoazo series: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269
디스아조계: 피그먼트 레드 37, 38, 41Disazo system: Pigment Red 37, 38, 41
모노아조레이크계: 피그먼트 레드 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68.48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.
벤즈이미다졸론계: 피그먼트 레드 171, 피그먼트 레드 175, 피그먼트 레드 176, 피그먼트 레드 185, 피그먼트 레드 208Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208
페릴렌계: 솔벤트 레드 135, 솔벤트 레드 179, 피그먼트 레드 123, 피그먼트 레드 149, 피그먼트 레드 166, 피그먼트 레드 178, 피그먼트 레드 179, 피그먼트 레드 190, 피그먼트 레드 194, 피그먼트 레드 224Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224
디케토피롤로피롤계: 피그먼트 레드 254, 피그먼트 레드 255, 피그먼트 레드 264, 피그먼트 레드 270, 피그먼트 레드 272Diketopyrrolopyrrole system: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272
축합 아조계: 피그먼트 레드 220, 피그먼트 레드 144, 피그먼트 레드 166, 피그먼트 레드 214, 피그먼트 레드 220, 피그먼트 레드 221, 피그먼트 레드 242Condensation azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242
안트라퀴논계: 피그먼트 레드 168, 피그먼트 레드 177, 피그먼트 레드 216, 솔벤트 레드 149, 솔벤트 레드 150, 솔벤트 레드 52, 솔벤트 레드 207Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207
퀴나크리돈계: 피그먼트 레드 122, 피그먼트 레드 202, 피그먼트 레드 206, 피그먼트 레드 207, 피그먼트 레드 209Quinacridone system: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209
기타, 색조를 조정할 목적으로, 보라색, 오렌지색, 갈색, 흑색 등의 착색제를 가할 수도 있다.In addition, coloring agents such as purple, orange, brown, and black may be added for the purpose of adjusting the color tone.
구체적으로는, 예를 들면 보라색 착색제로서는 피그먼트 바이올렛 19, 23, 29, 32, 36, 38, 42, 솔벤트 바이올렛 13, 36, 오렌지 착색제로서는 피그먼트 오렌지 5, 피그먼트 오렌지 13, 피그먼트 오렌지 14, 피그먼트 오렌지 16, 피그먼트 오렌지 17, 피그먼트 오렌지 24, 피그먼트 오렌지 34, 피그먼트 오렌지 36, 피그먼트 오렌지 38, 피그먼트 오렌지 40, 피그먼트 오렌지 43, 피그먼트 오렌지 46, 피그먼트 오렌지 49, 피그먼트 오렌지 51, 피그먼트 오렌지 61, 피그먼트 오렌지 63, 피그먼트 오렌지 64, 피그먼트 오렌지 71, 피그먼트 오렌지 73, 갈색 착색제로서는 피그먼트 브라운 23, 피그먼트 브라운 25, 흑색 착색제로서는 피그먼트 블랙 1, 피그먼트 블랙 7 등을 들 수 있다.Specifically, for example, pigment violet 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36 as a purple colorant, pigment orange 5, pigment orange 13, pigment orange 14 as an orange colorant. , Pigment Orange 16, Pigment Orange 17, Pigment Orange 24, Pigment Orange 34, Pigment Orange 36, Pigment Orange 38, Pigment Orange 40, Pigment Orange 43, Pigment Orange 46, Pigment Orange 49 Pigment Orange 51, Pigment Orange 61, Pigment Orange 63, Pigment Orange 64, Pigment Orange 71, Pigment Orange 73, Pigment Brown 23, Pigment Brown 25, Brown Black as Pigment Black 1, pigment black 7, etc. are mentioned.
이러한 착색제의 배합 비율은 특별히 제한은 없지만, 특성에 영향을 주지 않고 원하는 착색을 얻기 위해서 카르복실기 함유 수지 100 질량부에 대하여 0 내지 10 질량부인 것이 바람직하다. 보다 바람직하게는 0.1 내지 5 질량부이다.Although the compounding ratio of such a coloring agent does not have a restriction | limiting in particular, It is preferable that it is 0-10 mass parts with respect to 100 mass parts of carboxyl group-containing resin in order to obtain desired coloring, without affecting a characteristic. More preferably, it is 0.1-5 mass parts.
본 실시 형태의 광경화성 수지 조성물에는 산화를 막기 위해서 산화 방지제를 첨가할 수도 있다. 고분자 재료의 대부분은 한번 산화가 시작되면 차례차례로 연쇄적으로 산화 열화가 일어나, 고분자 소재의 기능 저하를 가져오는 것으로부터, 발생한 라디칼을 무효화하는 라디칼 포착제나, 발생한 과산화물을 무해한 물질로 분해하고, 새로운 라디칼이 발생하지 않도록 하는 과산화물 분해제 등의 산화 방지제가 유효하다.In order to prevent oxidation, you may add antioxidant to the photocurable resin composition of this embodiment. Most of the polymer materials are oxidatively deteriorated in sequence once oxidation starts, resulting in deterioration of the function of the polymer material, decomposing the radical scavenger that invalidates the generated radicals, and decomposing the generated peroxide into a harmless substance. Antioxidants, such as a peroxide decomposer which prevents a radical from generating, are effective.
라디칼 포착제로서 기능하는 산화 방지제로서는, 구체적으로는 예를 들면 히드로퀴논, 4-tert-부틸카테콜, 2-t-부틸히드로퀴논, 히드로퀴논모노메틸에테르, 2,6-디-t-부틸-p-크레졸, 2,2-메틸렌-비스-(4-메틸-6-t-부틸페놀), 1,1,3-트리스(2-메틸-4-히드록시-5-t-부틸페닐)부탄, 1,3,5-트리메틸-2,4,6-트리스(3,5-디-t-부틸-4-히드록시벤질)벤젠, 1,3,5-트리스(3',5'디-t-부틸-4-히드록시벤질)-S-트리아진-2,4,6-(1H,3H,5H)트리온 등의 페놀계, 메타퀴논, 벤조퀴논 등의 퀴논계 화합물, 비스(2,2,6,6-테트라메틸-4-피페리딜)-세바케이트, 페노티아진 등의 아민계 화합물 등을 들 수 있다.Specifically as antioxidant which functions as a radical trapping agent, hydroquinone, 4-tert- butylcatechol, 2-t- butyl hydroquinone, hydroquinone monomethyl ether, 2, 6- di-t- butyl- p- Cresol, 2,2-methylene-bis- (4-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1 , 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'di-t- Phenolic compounds, such as butyl-4-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds, such as metaquinone and benzoquinone, bis (2,2) And amine compounds such as 6,6-tetramethyl-4-piperidyl) -sebacate and phenothiazine.
라디칼 포착제는 시판되고 있는 것이어도 되고, 구체적으로는 예를 들면 아데카사 제조의 아데카스탭(등록상표) AO-30, 아데카스탭 AO-330, 아데카스탭 AO-20, 아데카스탭 LA-77, 아데카스탭 LA-57, 아데카스탭 LA-67, 아데카스탭 LA-68, 아데카스탭 LA-87, 바스프 재팬사 제조의 이르가녹스(IRGANOX; 등록상표) 1010, 이르가녹스 1035, 이르가녹스 1076, 이르가녹스 1135, 티누빈(TINUVIN; 등록상표) 111FDL, 티누빈 123, 티누빈 144, 티누빈 152, 티누빈 292, 티누빈 5100 등을 들 수 있다.A radical scavenger may be commercially available, and specifically, it can be used for example, adecas tab (trademark) AO-30 by Adeka Corporation, adecas tab AO-330, adecas tab AO-20, adecas tab LA -77, adecastab LA-57, adecastab LA-67, adecastab LA-68, adecastab LA-87, Irganox (IRGANOX (registered trademark) 1010, Irganox made by BASF Japan) 1035, Irganox 1076, Irganox 1135, TINUVIN® 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 and the like.
과산화물 분해제로서 기능하는 산화 방지제로서는, 구체적으로는 예를 들면 트리페닐포스파이트 등의 인계 화합물, 펜타에리트리톨테트라라우릴티오프로피오네이트, 디라우릴티오디프로피오네이트, 디스테아릴3,3'-티오디프로피오네이트 등의 황계 화합물 등을 들 수 있다.Specifically as antioxidant which functions as a peroxide decomposer, For example, phosphorus compounds, such as a triphenyl phosphite, pentaerythritol tetralauryl thio propionate, the dilauryl thiodipropionate, distearyl 3,3 Sulfur type compounds, such as "-thiodipropionate, etc. are mentioned.
과산화물 분해제는 시판되고 있는 것일 수도 있고, 구체적으로는 예를 들면 아데카사 제조의 아데카스탭 TPP, 아데카·아구스 가가꾸 제조의 마크 AO-412S, 스미또모 가가꾸 제조의 스밀라이저(등록상표) TPS 등을 들 수 있다.The peroxide decomposer may be commercially available, and specifically, for example, Adecas tab TPP manufactured by Adeka Co., Mark AO-412S by Adeka Agus Chemical Co., Ltd., and a smistizer manufactured by Sumitomo Chemical Co., Ltd. ) TPS, etc. are mentioned.
이들 산화 방지제는 단독으로 또는 2종 이상을 병용할 수 있다.These antioxidants can be used alone or in combination of two or more.
또한, 본 실시 형태의 광경화성 수지 조성물에 있어서, 추가로 자외선 흡수제를 가할 수도 있다. 고분자 재료는 광을 흡수하고, 그에 의해 분해·열화를 일으키는 것으로부터, 자외선에 대한 안정화 대책이 유효하다.Moreover, in the photocurable resin composition of this embodiment, a ultraviolet absorber can also be added further. Since the polymer material absorbs light and causes decomposition and deterioration, a stabilization measure against ultraviolet rays is effective.
자외선 흡수제로서는 예를 들면 벤조페논 유도체, 벤조에이트 유도체, 벤조트리아졸 유도체, 트리아진 유도체, 벤조티아졸 유도체, 신나메이트 유도체, 안트라닐레이트 유도체, 디벤조일메탄 유도체, 쿠마린 유도체 등을 들 수 있다.As a ultraviolet absorber, a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, an anthranilate derivative, a dibenzoyl methane derivative, a coumarin derivative, etc. are mentioned, for example.
벤조페논 유도체로서는, 구체적으로는 예를 들면 2-히드록시-4-메톡시-벤조페논 2-히드록시-4-메톡시벤조페논, 2-히드록시-4-n-옥톡시벤조페논, 2,2'-디히드록시-4-메톡시벤조페논 및 2,4-디히드록시벤조페논 등을 들 수 있다.Specific examples of the benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2 2, 4- dihydroxy-4- methoxy benzophenone, 2, 4- dihydroxy benzophenone, etc. are mentioned.
벤조에이트 유도체로서는, 구체적으로는 예를 들면 2-에틸헥실살리실레이트, 페닐살리실레이트, p-tert-부틸페닐살리실레이트, 2,4-디-tert-부틸페닐-3,5-디-tert-부틸-4-히드록시벤조에이트 및 헥사데실-3,5-디-tert-부틸-4-히드록시벤조에이트 등을 들 수 있다.Specific examples of the benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di -tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, and the like.
벤조트리아졸 유도체로서는, 구체적으로는 예를 들면 2-(2'-히드록시-5'-t-부틸페닐)벤조트리아졸, 2-(2'-히드록시-5'-메틸페닐)벤조트리아졸, 2-(2'-히드록시-3'-tert-부틸-5'-메틸페닐)-5-클로로벤조트리아졸, 2-(2'-히드록시-3',5'-디-tert-부틸페닐)-5-클로로벤조트리아졸, 2-(2'-히드록시-5'-메틸페닐)벤조트리아졸 및 2-(2'-히드록시-3',5'-디-tert-아밀페닐)벤조트리아졸을 들 수 있다.Specific examples of the benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole. , 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl Phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) Benzotriazole is mentioned.
트리아진 유도체로서는, 구체적으로는 예를 들면 히드록시페닐트리아진, 비스에틸헥실옥시페놀메톡시페닐트리아진 등을 들 수 있다.Specific examples of the triazine derivatives include hydroxyphenyltriazine, bisethylhexyloxyphenol methoxyphenyltriazine, and the like.
이러한 자외선 흡수제로서는 시판되고 있는 것이어도 되고, 구체적으로는 예를 들면 바스프 재팬사 제조의 티누빈 PS, 티누빈 99-2, 티누빈 109, 티누빈 384-2, 티누빈 900, 티누빈 928, 티누빈 1130, 티누빈 400, 티누빈 405, 티누빈 460, 티누빈 479 등을 들 수 있다.As such a ultraviolet absorber, what is marketed may be sufficient, Specifically, For example, Tinuvin PS, Tinuvin 99-2, Tinuvin 109, Tinuvin 384-2, Tinuvin 900, Tinuvin 928 by BASF Japan Co., Ltd., Tinuvin 1130, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 479, etc. are mentioned.
이들 자외선 흡수제는 단독으로 또는 2종 이상을 병용할 수 있고, 산화 방지제와 병용함으로써 본 실시 형태의 광경화성 수지 조성물로부터 얻어지는 경화물의 안정화를 도모할 수 있다.These ultraviolet absorbers can be used individually or in combination of 2 or more types, and can stabilize stabilization of the hardened | cured material obtained from the photocurable resin composition of this embodiment by using together with antioxidant.
본 실시 형태의 광경화성 수지 조성물은 필요에 따라서 충전재를 배합할 수 있다. 이러한 충전재로서는 공지된 무기 또는 유기 충전재를 사용할 수 있다.The photocurable resin composition of this embodiment can mix | blend a filler as needed. As such a filler, a known inorganic or organic filler can be used.
도막의 물리적 강도 등을 높이기 위해서는, 특히 황산바륨, 구상 실리카 및 탈크가 바람직하게 이용된다.In order to raise the physical strength of a coating film, etc., especially barium sulfate, spherical silica, and talc are used preferably.
또한, 백색의 외관이나 난연성을 얻기 위해서, 산화티탄이나 금속 산화물, 수산화 알루미늄등의 금속 수산화물을 체질 안료 충전재로서 사용할 수 있다.Moreover, in order to acquire a white appearance and flame retardance, metal hydroxides, such as a titanium oxide, a metal oxide, and aluminum hydroxide, can be used as a extender pigment filler.
이러한 충전재의 배합량은 조성물 전체량의 75 질량% 이하인 것이 바람직하다. 충전재의 배합량이 조성물 전체량의 75 질량%를 초과한 경우, 절연 조성물의 점도가 높아져서 도포, 성형성이 저하되거나, 경화물이 취약해진다. 보다 바람직하게는 0.1 내지 60 질량%의 비율이다.It is preferable that the compounding quantity of such a filler is 75 mass% or less of the whole composition. When the blending amount of the filler exceeds 75 mass% of the total amount of the composition, the viscosity of the insulating composition becomes high, and the coating and the formability are lowered, and the cured product becomes fragile. And more preferably 0.1 to 60 mass%.
본 실시 형태의 광경화성 수지 조성물은 또한 필요에 따라서 미분 실리카, 유기 벤토나이트, 몬모릴로나이트, 히드로탈사이트 등의 틱소트로픽화제를 첨가할 수 있다. 틱소트로픽화제로서의 경시 안정성은 유기 벤토나이트, 히드로탈사이트가 바람직하고, 특히 히드로탈사이트는 전기 특성이 우수하다.The photocurable resin composition of this embodiment can also add thixotropic agents, such as fine-grained silica, organic bentonite, montmorillonite, hydrotalcite, etc. as needed. The aging stability as a thixotropic agent is preferably organic bentonite or hydrotalcite, and particularly hydrotalcite has excellent electrical properties.
또한, 열중합 금지제나, 실리콘계, 불소계, 고분자계 등의 소포제 및/또는 레벨링제, 이미다졸계, 티아졸계, 트리아졸계 등의 실란 커플링제, 방청제 등과 같은 공지된 첨가제류를 배합할 수 있다.Moreover, well-known additives, such as a thermal polymerization inhibitor, antifoamers and / or leveling agents, such as a silicone type, a fluorine type, a polymeric type, a silane coupling agent, such as an imidazole type, a thiazole type, a triazole type, and a rust inhibitor, can be mix | blended.
또한, 본 실시 형태의 광경화성 수지 조성물은 카르복실기 함유 수지의 합성이나 조성물의 제조를 위해, 또는 기판이나 캐리어 필름에 도포하기 위한 점도 조정을 위해 유기 용제를 사용할 수 있다.Moreover, the organic solvent can be used for the photocurable resin composition of this embodiment for the synthesis | combination of carboxyl group-containing resin, manufacture of a composition, or viscosity adjustment for apply | coating to a board | substrate or a carrier film.
이러한 유기 용제로서는 케톤류, 방향족 탄화수소류, 글리콜에테르류, 글리콜에테르아세테이트류, 에스테르류, 알코올류, 지방족 탄화수소, 석유계 용제 등을 들 수 있다. 구체적으로는 예를 들면 메틸에틸케톤, 시클로헥사논 등의 케톤류; 톨루엔, 크실렌, 테트라메틸벤젠 등의 방향족 탄화수소류; 셀로솔브, 메틸셀로솔브, 부틸셀로솔브, 카르비톨, 메틸카르비톨, 부틸카르비톨, 프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노메틸에테르, 디프로필렌글리콜디에틸에테르, 트리에틸렌글리콜모노에틸에테르 등의 글리콜에테르류; 아세트산에틸, 아세트산부틸, 디프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜에틸에테르아세테이트, 프로필렌글리콜부틸에테르아세테이트 등의 에스테르류; 에탄올, 프로판올, 에틸렌글리콜, 프로필렌글리콜 등의 알코올류; 옥탄, 데칸 등의 지방족 탄화수소; 석유 에테르, 석유 나프타, 수소 첨가 석유 나프타, 솔벤트 나프타 등의 석유계 용제 등을 들 수 있다. 이러한 유기 용제는 단독으로 또는 2종 이상의 혼합물로서 이용된다.Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like. Specifically, For example, ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether And the like; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents are used alone or as a mixture of two or more kinds.
본 실시 형태의 광경화성 수지 조성물은 또한 필요에 따라서 공지된 열중합 금지제, 미분 실리카, 유기 벤토나이트, 몬모릴로나이트 등의 증점제, 실리콘계, 불소계, 고분자계 등의 소포제, 레벨링제, 이미다졸계, 티아졸계, 트리아졸계 등의 실란 커플링제, 방청제 등의 첨가제류를 배합할 수 있다.The photocurable resin composition of the present embodiment may further contain known thermal polymerization inhibitors, finely divided silicas, thickeners such as organic bentonite and montmorillonite, antifoaming agents such as silicones, fluorine and polymers, leveling agents, imidazoles, and thiazoles. Additives, such as a silane coupling agent and a rust inhibitor, such as a triazole type, can be mix | blended.
이 중, 열중합 금지제는 중합성 화합물의 열적인 중합 또는 경시적인 중합을 방지하기 위해서 사용할 수 있다. 열중합 금지제로서는, 구체적으로는 예를 들면 4-메톡시페놀, 히드로퀴논, 알킬 또는 아릴 치환 히드로퀴논, t-부틸카테콜, 피로갈롤, 2-히드록시벤조페논, 4-메톡시-2-히드록시벤조페논, 염화제1구리, 페노티아진, 클로라닐, 나프틸아민, β-나프톨, 2,6-디-t-부틸-4-크레졸, 2,2'-메틸렌비스(4-메틸-6-t-부틸페놀), 피리딘, 니트로벤젠, 디니트로벤젠, 피크르산, 4-톨루이딘, 메틸렌블루, 구리와 유기 킬레이트제 반응물, 살리실산메틸, 및 페노티아진, 니트로소 화합물, 니트로소 화합물과 Al과의 킬레이트 등을 들 수 있다.Among these, a thermal polymerization inhibitor can be used in order to prevent thermal superposition | polymerization or superposition | polymerization superposition | polymerization of a polymeric compound. Specific examples of thermal polymerization inhibitors include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone and 4-methoxy-2-hydride. Roxybenzophenone, cuprous chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis (4-methyl- 6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and Al And chelate with.
본 실시 형태의 광경화성 수지 조성물은 소정의 배합비로 제조되고, 예를 들면 유기 용제에 의해 도포 방법에 적합한 점도가 되도록 조정된 후, 침지 코팅법, 플로우 코팅법, 롤 코팅법, 바 코터법, 스크린 인쇄법, 커튼 코팅법 등의 방법에 의해, 기재 상에 도포된다.The photocurable resin composition of this embodiment is manufactured by predetermined | prescribed compounding ratio, for example, it adjusts to the viscosity suitable for an application | coating method with the organic solvent, and then immersion coating method, flow coating method, roll coating method, bar coater method, It is apply | coated on a base material by methods, such as a screen printing method and a curtain coating method.
기재로서는 미리 회로 형성된 인쇄 배선판이나 플렉시블 인쇄 배선판 외에, 종이-페놀 수지, 종이-에폭시 수지, 유리천-에폭시 수지, 유리-폴리이미드, 유리천/부직포-에폭시 수지, 유리천/종이-에폭시 수지, 합성 섬유-에폭시 수지, 불소 수지·폴리에틸렌·PPO·시아네이트에스테르 등의 복합재를 이용한 모든 등급(FR-4 등)의 동장 적층판, 폴리이미드 필름, PET 필름, 유리 기판, 세라믹 기판, 웨이퍼판 등을 사용할 수 있다.As a base material, in addition to the printed wiring board and flexible printed wiring board which were formed beforehand, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / nonwoven fabric-epoxy resin, glass cloth / paper-epoxy resin, Copper clad laminates, polyimide films, PET films, glass substrates, ceramic substrates, wafer boards of all grades (FR-4, etc.) using composite materials such as synthetic fibers-epoxy resins, fluororesins, polyethylene, PPO, and cyanate esters Can be used.
그리고, 약 60 내지 100℃의 온도에서 조성물 중에 포함되는 유기 용제를 휘발 건조(가건조)시킴으로써 태크프리의 건조 도막이 형성된다.And the tack free dry coating film is formed by volatilizing (temporarily drying) the organic solvent contained in a composition at the temperature of about 60-100 degreeC.
이 때, 휘발 건조는 열풍 순환식 건조로, IR로, 핫 플레이트, 컨백션 오븐 등, 증기에 의한 공기 가열 방식의 열원을 구비한 것을 이용하여 건조기 내의 열풍을 향류 접촉시키는 방법 및 노즐로부터 지지체에 분무하는 방법을 이용하여 행할 수 있다.At this time, the volatilization drying is a hot air circulating drying furnace, an IR furnace, a hot plate, a convection oven, or the like, which has a heat source such as a hot air heating system by steam, and makes a countercurrent contact with the hot air in the dryer and from the nozzle to the support. It can carry out using the method of spraying.
그 후, 도막 상에 다이렉트 노광이나 분할 투영 노광 등에 의해 선택적으로 활성 에너지선을 조사하여 노광부를 광경화시킨다.Thereafter, active energy rays are selectively irradiated onto the coating film by direct exposure, divided projection exposure, or the like to photocure the exposed portion.
이 때, 활성 에너지선 조사에 이용되는 노광기로서는 직접 묘화 장치(예를 들면 컴퓨터로부터의 CAD 데이터에 의해 직접 레이저로 화상을 그리는 레이저 다이렉트 이미징 장치), (초)고압 수은 램프 등의 자외선 램프를 사용한 직접 묘화 장치를 사용할 수 있다. 이러한 직접 묘화 장치로서는, 예를 들면 닛본 오르보테크사 제조, 팬탁스사 제조 등의 것을 사용할 수 있다. 기타, 메탈할라이드 램프를 탑재한 노광기, (초)고압 수은 램프를 탑재한 노광기, 수은 쇼트 아크 램프를 탑재한 노광기 등을 사용할 수 있다.At this time, as an exposure machine used for active energy ray irradiation, a UV device such as a direct drawing device (for example, a laser direct imaging device for drawing an image with a laser directly by CAD data from a computer) and an ultra-high pressure mercury lamp are used. You can use a drawing device directly. As such a direct drawing apparatus, things, such as the Nippon Orbotech company make and the Pantax company make, can be used, for example. In addition, an exposure machine equipped with a metal halide lamp, an exposure machine equipped with a (ultra) high pressure mercury lamp, an exposure machine equipped with a mercury short arc lamp, and the like can be used.
활성 에너지선으로서는 피크 파장이 본 실시 형태의 광경화성 수지 조성물이 충분한 광흡수능을 갖는 300 내지 450 nm의 범위이면 된다. 또한, 레이저를 이용한 경우, 이 범위의 파장의 레이저광을 발진하는 것이면, 가스 레이저, 고체 레이저 등 매체는 특별히 한정되지 않다.As an active energy ray, peak wavelength should just be the range of 300-450 nm in which the photocurable resin composition of this embodiment has sufficient light absorption ability. In the case of using a laser, a medium such as a gas laser or a solid laser is not particularly limited as long as it emits laser light having a wavelength in this range.
또한, 그의 노광량은 막두께 등에 따라서 다르지만, 일반적으로는 5 내지 200 mJ/㎠, 본 실시 형태의 광경화성 수지 조성물에 있어서는, 특히 고감도가 얻어지는 것으로부터, 바람직하게는 5 내지 100 mJ/㎠, 더욱 바람직하게는 5 내지 50 mJ/㎠의 범위 내로 할 수 있다.Moreover, although the exposure amount changes with film thickness etc., in general, in the photocurable resin composition of 5-200 mJ / cm <2> and this embodiment, since especially high sensitivity is obtained, Preferably it is 5-100 mJ / cm <2>, More Preferably it can be in the range of 5-50 mJ / cm <2>.
그리고, 미노광부를 희알칼리 수용액에 의해 현상하여 레지스트 패턴이 형성된다. 현상 방법으로서는 디핑법, 샤워법, 스프레이법, 브러시법 등을 사용할 수 있다. 현상액으로서는 수산화칼륨, 수산화나트륨, 탄산나트륨, 탄산칼륨, 인산나트륨, 규산나트륨, 암모니아, 아민류 등의 희알칼리 수용액을 사용할 수 있다. 구체적으로는, 예를 들면 0.3 내지 3 중량% 탄산나트륨 수용액을 사용할 수 있다.Then, the unexposed portion is developed with a dilute alkaline aqueous solution to form a resist pattern. As a developing method, the dipping method, the shower method, the spray method, the brush method, etc. can be used. As a developing solution, aqueous alkali solution, such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, can be used. Specifically, 0.3-3 weight% sodium carbonate aqueous solution can be used, for example.
또한, 예를 들면 약 140 내지 180℃의 온도로 가열하여 열경화시키는 것이 바람직하다. 열경화에 의해 카르복실기 함유 수지의 카르복실기와, 분자 중에 2개 이상의 환상 에테르기 및/또는 환상 티오에테르기를 갖는 열경화 수지 등의 열경화성 성분이 반응하여, 내열성, 내약품성, 내흡습성, 밀착성, 전기 특성 등을 향상시키는 것이 가능해진다.In addition, it is preferable to heat to a temperature of, for example, about 140 to 180 ℃ to thermoset. By thermosetting, the carboxyl group of the carboxyl group-containing resin and a thermosetting component such as a thermosetting resin having two or more cyclic ether groups and / or cyclic thioether groups react with each other, and thus heat resistance, chemical resistance, hygroscopicity, adhesion, and electrical properties. Etc., it becomes possible to improve.
또한, 본 실시 형태의 광경화성 수지 조성물을 상술한 바와 같이 기재 상에 직접 도포하지 않고, 예를 들면 미리 필름 상에 도포하고, 건조시킨 건조 도막을 필름으로서 권취하고, 드라이 필름으로서 기재 상에 접합시킬 수도 있다.In addition, the photocurable resin composition of this embodiment is not apply | coated directly on a base material as mentioned above, For example, it coats previously on a film, and winds up the dried coating film dried as a film, and bonds on a base material as a dry film You can also
드라이 필름은, 예를 들면 캐리어 필름과, 솔더 레지스트층(광경화성 수지 조성물층)과, 필요에 따라서 이용되는 박리 가능한 커버 필름이 이 순서로 적층된 구조를 갖는 것이다. 캐리어 필름 상에 솔더 레지스트층을 형성 후, 필요에 따라서 커버 필름을 그 위에 적층하거나, 커버 필름 상에 솔더 레지스트층을 형성한 후, 이 적층체를 캐리어 필름에 적층함으로써 드라이 필름이 얻어진다.A dry film has a structure which the carrier film, the soldering resist layer (photocurable resin composition layer), and the peelable cover film used as needed are laminated | stacked in this order, for example. After forming a soldering resist layer on a carrier film, a cover film is laminated | stacked on it as needed, or after forming a soldering resist layer on a cover film, a dry film is obtained by laminating | stacking this laminated body to a carrier film.
이 때, 캐리어 필름으로서는 2 내지 150 ㎛의 두께의 폴리에틸렌테레프탈레이트, 폴리에스테르 필름 등의 열가소성 필름이 이용된다.At this time, as a carrier film, thermoplastic films, such as polyethylene terephthalate and a polyester film, whose thickness is 2-150 micrometers are used.
또한, 솔더 레지스트층은 광경화성 수지 조성물을 블레이드코터, 립코터, 코머코터, 필름코터 등으로 캐리어 필름 또는 커버 필름에 10 내지 150 ㎛의 두께로 균일하게 도포하고, 건조하여 형성된다.In addition, the solder resist layer is formed by uniformly applying a photocurable resin composition to a carrier film or a cover film with a blade coater, a lip coater, a coater coater, a film coater, etc. in a thickness of 10 to 150 ㎛, and dried.
그리고, 커버 필름으로서는 폴리에틸렌 필름, 폴리프로필렌 필름 등을 사용할 수 있는데, 솔더 레지스트층과의 접착력이 캐리어 필름보다도 작은 것이 좋다.And although a polyethylene film, a polypropylene film, etc. can be used as a cover film, it is good that adhesive force with a soldering resist layer is smaller than a carrier film.
이러한 드라이 필름을 이용하여, 예를 들면 이하와 같이 하여 인쇄 배선판 상에 보호막(영구 보호막)을 제작할 수 있다. 우선, 필요에 따라서 커버 필름을 박리하고, 솔더 레지스트층과 인쇄 기판을 중첩시키고, 또한 라미네이터 등을 이용하여 접합시킴으로써 인쇄 배선판 상에 솔더 레지스트층을 형성한다. 그리고, 솔더 레지스트층에 대하여 노광, 현상 및 가열 경화를 행함으로써 보호막(영구 보호막)이 형성된다. 또한, 캐리어 필름은 노광 전 또는 노광 후 중 어느 하나에서 박리하면 된다.Using such a dry film, a protective film (permanent protective film) can be produced on a printed wiring board as follows, for example. First, a cover film is peeled off as needed, a soldering resist layer and a printed circuit board overlap, and a soldering resist layer is formed on a printed wiring board by bonding together using a laminator or the like. And a protective film (permanent protective film) is formed by performing exposure, image development, and heat-hardening with respect to a soldering resist layer. In addition, what is necessary is just to peel a carrier film before exposure or after exposure.
이하, 실시예 및 비교예에 의해 본 실시 형태에 대해서 구체적으로 설명하는데, 본 발명이 이들 실시예에 한정되는 것은 아닌 것은 물론이다. 또한, 이하에서 「부」 및 「%」라고 되어있는 것은 특별한 언급이 없는 한 전부 질량 기준이다.Hereinafter, although an Example and a comparative example demonstrate this embodiment concretely, it cannot be overemphasized that this invention is not limited to these Examples. In addition, below, "part" and "%" are all mass references | standards unless there is particular notice.
(합성예 1)(Synthesis Example 1)
온도계, 교반기, 적하 깔때기 및 환류 냉각기를 구비한 플라스크에 용매로서 디프로필렌글리콜모노메틸에테르 325.0부를 110℃까지 가열하고, 메타크릴산 174.0부, ε-카프로락톤 변성 메타크릴산(평균 분자량 314) 174.0부, 메타크릴산메틸 77.0부, 디프로필렌글리콜모노메틸에테르 222.0부 및 중합 촉매로서 t-부틸퍼옥시2-에틸헥사노에이트(니찌유사 제조의 퍼부틸(등록상표) O) 12.0부의 혼합물을, 3시간에 걸쳐서 적하하고, 또한 110℃에서 3시간 교반하여, 중합 촉매를 실활시켜, 수지 용액을 얻었다.In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 325.0 parts of dipropylene glycol monomethyl ether as a solvent was heated to 110 ° C, 174.0 parts of methacrylic acid and ε-caprolactone modified methacrylic acid (average molecular weight 314) 174.0 A mixture of 77.0 parts of methyl methacrylate, 222.0 parts of dipropylene glycol monomethyl ether, and 12.0 parts of t-butylperoxy 2-ethylhexanoate (Perbutyl® O manufactured by Nichi Corporation) as a polymerization catalyst, It dripped over 3 hours, and also stirred at 110 degreeC for 3 hours, deactivated the polymerization catalyst, and obtained the resin solution.
이 수지 용액을 냉각 후, 다이셀 가가꾸 고교사 제조의 사이클로머-A200을 289.0부, 트리페닐포스핀 3.0부, 히드로퀴논모노메틸에테르 1.3부를 가하고, 100℃로 승온하고, 교반함으로써 에폭시기의 개환부가 반응을 행하여 감광성의 카르복실기 함유 수지 용액 (B-1)을 얻었다.After cooling this resin solution, 289.0 parts of cyclocel-A200 manufactured by Daicel Chemical Industries, Ltd., 3.0 parts of triphenylphosphine, and 1.3 parts of hydroquinone monomethyl ether were added, and the ring opening part of an epoxy group was heated and stirred at 100 degreeC. The reaction was carried out to obtain a photosensitive carboxyl group-containing resin solution (B-1).
이와 같이 하여 얻어진 수지 용액 (B-1)은 중량 평균 분자량(Mw)이 15,000이고, 또한 고형분이 57%, 고형물의 산가가 79.8 mgKOH/g이었다.The resin solution (B-1) thus obtained had a weight average molecular weight (Mw) of 15,000, a solid content of 57%, and an acid value of solids of 79.8 mgKOH / g.
또한, 얻어진 수지의 중량 평균 분자량은 시마즈 세이사꾸쇼사 제조의 펌프 LC-6AD와, 쇼와 덴꼬사 제조의 칼럼(쇼덱스(Shodex; 등록상표) KF-804, KF-803, KF-802)을 3개 연결한 고속 액체 크로마토그래피에 의해 측정하였다.In addition, the weight average molecular weight of obtained resin was the pump LC-6AD by the Shimadzu Corporation Corporation, and the column (Shodex (trademark) KF-804, KF-803, KF-802) by Showa Denko Co., Ltd.). It was measured by high performance liquid chromatography of three connected.
(합성예 2)(Synthesis Example 2)
온도계, 교반기, 적하 깔때기 및 환류 냉각기를 구비한 삼구 플라스크에 메틸메타크릴레이트 200부, 글리시딜메타크릴레이트 142부, 디에틸렌글리콜모노에틸에테르아세테이트 300부를 투입하고, 촉매로서 아조비스이소부티로니트릴을 가하고, 교반하면서 80℃에서 10시간 반응시켰다.200 parts of methyl methacrylate, 142 parts of glycidyl methacrylate, and 300 parts of diethylene glycol monoethyl ether acetate were added to a three neck flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, and azobisisobutyro was used as a catalyst. Nitrile was added and reacted at 80 degreeC for 10 hours, stirring.
그리고, 메타크릴산 88부, 트리페닐포스핀 2.0부, 안정제로서 히드로퀴논 0.2부를 달아 취하고, 적하 깔때기로 적하하고, 80℃에서 16시간 반응시켰다. 또한 테트라히드로무수프탈산 140부를 첨가하고, 80℃에서 5시간 반응시켜 감광성의 카르복실기 함유 수지 용액 (B-2)을 얻었다.Then, 88 parts of methacrylic acid, 2.0 parts of triphenylphosphine and 0.2 part of hydroquinone were added as a stabilizer, added dropwise with a dropping funnel, and reacted at 80 ° C for 16 hours. Furthermore, 140 parts of tetrahydrophthalic anhydride were added, and it reacted at 80 degreeC for 5 hours, and obtained the photosensitive carboxyl group-containing resin solution (B-2).
이와 같이 하여 얻어진 수지 용액 (B-2)의 고형분은 65%, 고형분의 산가는 91 mgKOH/g이었다.Thus, the solid content of the resin solution (B-2) obtained was 65%, and the acid value of solid content was 91 mgKOH / g.
(합성예 3)(Synthesis Example 3)
온도계, 교반기 및 환류 냉각기를 구비한 5 리터의 세퍼러블 플라스크에 중합체 폴리올로서 폴리카프로락톤디올(다이셀 가가꾸 고교사 제조의 플락셀(PLACCEL)208, 분자량 830) 1,245 g, 카르복실기를 갖는 디히드록실 화합물로서 디메틸올프로피온산 201 g, 폴리이소시아네이트로서 이소포론디이소시아네이트 777 g 및 히드록실기를 갖는 (메트)아크릴레이트로서 2-히드록시에틸아크릴레이트 119 g, 또한 p-메톡시페놀 및 디-t-부틸-히드록시톨루엔을 각각 0.5 g씩 투입하였다.1,245 g of polycaprolactonediol (PLACCEL 208, molecular weight 830, manufactured by Daicel Chemical Industries, Ltd.) as a polymer polyol in a 5-liter separable flask equipped with a thermometer, a stirrer and a reflux condenser, and a dihydrate having a carboxyl group 201 g of dimethylolpropionic acid as a hydroxyl compound, 777 g of isophorone diisocyanate as a polyisocyanate and 119 g of 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group, and also p-methoxyphenol and di-t 0.5 g of each of -butyl-hydroxytoluene was added thereto.
교반하면서 60℃까지 가열하여 정지하고, 디부틸주석디라우레이트 0.8 g을 첨가하였다. 반응 용기 내의 온도가 저하하기 시작하면 재차 가열하고, 80℃에서 교반을 계속하고, 적외선 흡수 스펙트럼으로 이소시아네이트기의 흡수 스펙트럼(2280 cm-1)이 소실된 것을 확인하여 반응을 종료하여, 점조액체의 우레탄아크릴레이트 화합물을 얻었다. 카르비톨아세테이트를 이용하여 불휘발분=50 질량%로 조정하여 감광성의 카르복실기 함유 수지 용액 (B-3)을 얻었다.It stirred by heating to 60 degreeC, stirring, and 0.8 g of dibutyltin dilaurates were added. When the temperature in the reaction vessel starts to decrease, the mixture is heated again, and the stirring is continued at 80 ° C. The infrared absorption spectrum confirms that the absorption spectrum (2280 cm -1 ) of the isocyanate group is lost, and the reaction is terminated. The urethane acrylate compound was obtained. It adjusted to non volatile matter = 50 mass% using carbitol acetate, and obtained the photosensitive carboxyl group-containing resin solution (B-3).
이와 같이 하여 얻어진 수지 용액 (B-3)의 고형분은 50%, 고형분의 산가는 47 mgKOH/g이었다.Thus, the solid content of the resin solution (B-3) obtained was 50%, and the acid value of solid content was 47 mgKOH / g.
(합성예 4)(Synthesis Example 4)
디에틸렌글리콜모노에틸에테르아세테이트 600 g에 오르토크레졸노볼락형 에폭시 수지〔DIC사 제조의 에피클론 N-695, 연화점 95℃, 에폭시 당량 214, 평균 관능기수 7.6〕1070 g(글리시딜기수(방향환 총수): 5.0몰), 아크릴산 360 g(5.0몰) 및 히드로퀴논 1.5 g을 투입하고, 100℃로 가열 교반하여 균일 용해하였다.To 600 g of diethylene glycol monoethyl ether acetate orthocresol novolak type epoxy resin (Epiclon N-695 by DIC Corporation, softening point 95 degreeC, epoxy equivalent 214, average functional group number 7.6) 1070 g (glycidyl group number (direction Total number of rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid and 1.5 g of hydroquinone were added thereto, and the resulting mixture was dissolved by heating and stirring to 100 ° C.
이어서, 트리페닐포스핀 4.3 g을 투입하고, 110℃로 가열하여 2시간 반응 후, 120℃로 승온하고 추가로 12시간 반응을 행하였다. 얻어진 반응액에 방향족계 탄화수소(솔벳소 150) 415 g, 테트라히드로무수프탈산 456.0 g(3.0몰)을 투입하고, 110℃에서 4시간 반응을 행하고, 냉각하여 감광성의 카르복실기 함유 수지 용액 (B-4)을 얻었다.Then, 4.3 g of triphenylphosphine was added, and the mixture was heated to 110 ° C and reacted for 2 hours, then heated to 120 ° C and further reacted for 12 hours. 415 g of aromatic hydrocarbon (Solvso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction liquid, and reaction was performed at 110 degreeC for 4 hours, it cooled, and the photosensitive carboxyl group-containing resin solution (B-4) )
이와 같이 하여 얻어진 수지 용액 (B-4)의 고형분은 65%, 고형분의 산가는 89 mgKOH/g이었다.Thus, the solid content of the resin solution (B-4) obtained was 65%, and the acid value of solid content was 89 mgKOH / g.
(합성예 5)(Synthesis Example 5)
디에틸렌글리콜모노에틸에테르아세테이트 700 g에 오르토크레졸노볼락형 에폭시 수지(DIC사 제조의 에피클론-695, 연화점 95℃, 에폭시 당량 214, 평균 관능기수 7.6) 1070 g(글리시딜기수(방향환 총수): 5.0몰), 아크릴산 360 g(5.0몰) 및 히드로퀴논 1.5 g을 투입하고, 100℃로 가열 교반하여 균일 용해하였다.To 700 g of diethylene glycol monoethyl ether acetate orthocresol novolak type epoxy resin (Epiclon-695 by DIC Corporation, softening point 95 degreeC, epoxy equivalent 214, average functional group number 7.6) 1070 g (glycidyl group number (aromatic ring) Total number): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were added, and it heated and stirred at 100 degreeC, and melt | dissolved uniformly.
이어서, 트리페닐포스핀 4.3 g을 투입하고, 110℃로 가열하고 2시간 반응 후, 추가로 트리페닐포스핀 1.6 g을 추가하고, 120℃로 승온하고 추가로 12시간 반응을 행하였다. 얻어진 반응액에 방향족계 탄화수소(엑손 가가꾸 가부시끼가이샤 제조의 솔벳소 150) 562 g, 테트라히드로무수프탈산 684 g(4.5몰)을 투입하고, 110℃에서 4시간 반응을 행하였다. 또한, 얻어진 반응액에 글리시딜메타크릴레이트 142.0 g(1.0몰)을 투입하고, 115℃에서 4시간 반응을 행하여 감광성의 카르복실기 함유 수지 용액 (B-5)을 얻었다.Subsequently, 4.3 g of triphenylphosphines were added, and it heated at 110 degreeC, and after reaction for 2 hours, 1.6 g of triphenylphosphines were further added, it heated up at 120 degreeC, and also reacted for 12 hours. 562 g of aromatic hydrocarbons (Solvso 150 manufactured by Exxon Chemical Co., Ltd.) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were added to the reaction solution, and the reaction was carried out at 110 ° C for 4 hours. Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylates were thrown into the obtained reaction liquid, and it reacted at 115 degreeC for 4 hours, and obtained the photosensitive carboxyl group-containing resin solution (B-5).
이와 같이 하여 얻어진 수지 용액 (B-5)의 고형분은 65%, 고형분의 산가는 87 mgKOH/g이었다.Thus, the solid content of the resin solution (B-5) obtained was 65%, and the acid value of solid content was 87 mgKOH / g.
(합성예 6)(Synthesis Example 6)
에폭시 당량 800, 연화점 79℃의 비스페놀 F형 고형 에폭시 수지 400부를 에피클로로히드린 925부와 디메틸술폭시드 462.5부를 용해시킨 후, 교반 하 70℃에서 98.5% NaOH 81.2부를 100분에 걸쳐서 첨가하였다. 첨가 후, 추가로 70℃에서 3시간 반응을 행하였다.925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide were dissolved in 400 parts of bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 DEG C and then 81.2 parts of 98.5% NaOH was added thereto at 70 DEG C over 100 minutes while stirring. After addition, reaction was further performed at 70 degreeC for 3 hours.
이어서, 과잉의 미반응 에피클로로히드린 및 디메틸술폭시드의 대부분을 감압 하에 증류 제거하고, 부생염과 디메틸술폭시드를 포함하는 반응 생성물을 메틸이소부틸케톤 750부에 용해시키고, 또한 30% NaOH 10부를 가하고 70℃에서 1시간 반응시켰다. 반응 종료 후, 물 200부로 2회 수세를 행하였다. 유수 분리 후, 유층으로부터 메틸이소부틸케톤을 증류 회수하여 에폭시 당량 290, 연화점 62℃의 에폭시 수지 (a-1) 370부를 얻었다.Subsequently, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further, 30% NaOH 10 Part was added and reacted at 70 ° C for 1 hour. After completion of the reaction, water washing was performed twice with 200 parts of water. Methyl isobutyl ketone was distilled off from the oil layer after oil-water separation, and 370 parts of epoxy resins (a-1) of epoxy equivalent 290 and softening point 62 degreeC were obtained.
얻어진 에폭시 수지 (a-1) 2900부(10 당량), 아크릴산 720부(10 당량), 메틸히드로퀴논 2.8부, 카르비톨아세테이트 1950부를 투입하고, 90℃로 가열, 교반하여 반응 혼합물을 용해하였다. 이어서, 반응액을 60℃로 냉각하고, 트리페닐포스핀 16.7부를 투입하고, 100℃로 가열하여, 약 32시간 반응하여 산가가 1.0 mgKOH/g인 반응물을 얻었다. 다음으로, 이것에 무수 숙신산 786부(7.86몰), 카르비톨아세테이트 423부를 투입하고, 95℃로 가열하고, 약 6시간 반응을 행하여 감광성의 카르복실기 함유 수지 용액 (B-6)을 얻었다.2900 parts (10 equivalents) of obtained epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone, and 1950 parts of carbitol acetate were thrown in, and it heated and stirred at 90 degreeC, and dissolved the reaction mixture. Subsequently, the reaction solution was cooled to 60 ° C, 16.7 parts of triphenylphosphine was added, heated to 100 ° C, and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Next, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were put into this, it heated at 95 degreeC, and it reacted for about 6 hours, and obtained the photosensitive carboxyl group-containing resin solution (B-6).
이와 같이 하여 얻어진 수지 용액 (B-6)의 고형분은 65%, 고형분의 산가는 100 mgKOH/g이었다.Thus, the solid content of the resin solution (B-6) obtained was 65%, and the acid value of solid content was 100 mgKOH / g.
(합성예 7)(Synthesis Example 7)
온도계, 질소 도입 장치겸 알킬렌옥시드 도입 장치 및 교반 장치를 구비한 오토클레이브에 노볼락형 크레졸 수지(쇼와 고분시사 제조, 쇼놀 C RG951, OH 당량: 119.4) 119.4 g, 수산화칼륨 1.19 g 및 톨루엔 119.4 g을 투입하고, 교반하면서 계 내를 질소 치환하고, 가열 승온하였다.119.4 g of novolak-type cresol resin (Showa Chemical Co., Ltd., Shool C RG951, OH equivalents: 119.4) in an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device, and a stirring device, 1.19 g of potassium hydroxide, and 19.4 g was added, the inside of the system was purged with nitrogen while stirring, and the temperature was increased by heating.
다음으로, 프로필렌옥시드 63.8 g을 서서히 적하하고, 125 내지 132℃, 0 내지 4.8 kg/㎠로 16시간 반응시켰다. 그 후, 실온까지 냉각하고, 이 반응 용액에 89% 인산 1.56 g을 첨가 혼합하여 수산화칼륨을 중화하여, 불휘발분 62.1%, 수산기가가 182.2 g/eq.인 노볼락형 크레졸 수지의 프로필렌옥시드 반응 용액을 얻었다. 이것은, 페놀성 수산기 1 당량당 알킬렌옥시드가 평균 1.08몰 부가되어 있는 것이었다.Next, 63.8 g of propylene oxide was slowly added dropwise and reacted at 125 to 132 ° C and 0 to 4.8 kg / cm 2 for 16 hours. Thereafter, the mixture was cooled to room temperature, 1.56 g of 89% phosphoric acid was added to the reaction solution, mixed to neutralize potassium hydroxide, and propylene oxide of a novolak-type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. The reaction solution was obtained. This was an average of 1.08 mol of alkylene oxide added per equivalent of phenolic hydroxyl group.
얻어진 노볼락형 크레졸 수지의 알킬렌옥시드 반응 용액 293.0 g, 아크릴산 43.2 g, 메탄술폰산 11.53 g, 메틸히드로퀴논 0.18 g 및 톨루엔 252.9 g을 교반기, 온도계 및 공기 취입관을 구비한 반응기에 투입하고, 공기를 10 ml/분의 속도로 취입하고, 교반하면서 110℃에서 12시간 반응시켰다. 반응에 의해 생성된 물은 톨루엔과의 공비 혼합물로서 12.6 g의 물이 유출되었다.293.0 g of the alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was supplied. Blown at a rate of 10 ml / min, and reacted at 110 degreeC for 12 hours, stirring. The water produced by the reaction flowed out of 12.6 g of an azeotropic mixture with toluene.
그 후, 실온까지 냉각하고, 얻어진 반응 용액을 15% 수산화나트륨 수용액 35.35 g으로 중화하고, 이어서 수세하였다. 그 후, 증발기로 톨루엔을 디에틸렌글리콜모노에틸에테르아세테이트 118.1 g으로 치환하면서 증류 제거하여 노볼락형 아크릴레이트 수지 용액을 얻었다.Thereafter, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of an aqueous 15% sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while replacing toluene with 118.1 g of diethylene glycol monoethyl ether acetate to obtain a novolak-type acrylate resin solution.
다음으로, 얻어진 노볼락형 아크릴레이트 수지 용액 332.5 g 및 트리페닐포스핀 1.22 g을 교반기, 온도계 및 공기 취입관을 구비한 반응기에 투입하고, 공기를 10 ml/분의 속도로 취입하고, 교반하면서 테트라히드로프탈산 무수물 60.8 g을 서서히 가하고, 95 내지 101℃에서 6시간 반응시켜 감광성의 카르복실기 함유 수지 용액 (B-7)을 얻었다.Next, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air blown tube, and the air was blown at a rate of 10 ml / min and stirred. 60.8 g of tetrahydrophthalic anhydride was added gradually, it was made to react at 95-101 degreeC for 6 hours, and the photosensitive carboxyl group-containing resin solution (B-7) was obtained.
이와 같이 하여 얻어진 수지 용액 (B-7)의 고형분은 71%, 고형분의 산가는 88 mgKOH/g이었다.Thus, the solid content of the resin solution (B-7) obtained was 71%, and the acid value of solid content was 88 mgKOH / g.
또한, 수지 용액 B-8로서 시판품인 ZCR-1601H(닛본 가야꾸사 제조의 산가: 96 mgKOH/g, 고형분: 65%)를 그대로 이용하였다.In addition, ZCR-1601H (an acid value from Nippon Kayaku Co., Ltd .: 96 mgKOH / g, solid content: 65%) which is a commercial item was used as resin solution B-8 as it was.
이들 수지 용액 B-1 내지 B-8을 이용하여, 표 1에 나타내는 배합(질량부)으로 배합하고, 교반기로 예비 혼합한 후, 3축 롤밀로 혼련하여, 실시예 1 내지 8, 비교예 1, 2의 솔더 레지스트용 광경화성 수지 조성물을 제조하였다.Using these resin solutions B-1-B-8, it mix | blends with the compounding (mass part) shown in Table 1, pre-mixes with a stirrer, and knead | mixes with a triaxial roll mill, Examples 1-8 and Comparative Example 1 And 2, the photocurable resin composition for soldering resists was manufactured.
또한, 여기서 얻어진 광경화성 수지 조성물의 분산도를 에릭센사 제조의 그라인드미터에 의한 입도 측정으로 평가한 바, 각각 15 ㎛ 이하였다.In addition, when the dispersion degree of the photocurable resin composition obtained here was evaluated by the particle size measurement by the grinder made by Eriksen, it was 15 micrometers or less, respectively.
* 1: A-1* 1: A-1
* 2: A-2* 2: A-2
(바스프 재팬사 제조의 CGI-325)(CGI-325 made by BASF Japan company)
* 3: A-3 2메틸-1-(4-메틸티오페닐)-2모르폴리노프로판-1온* 3: A-3 2methyl-1- (4-methylthiophenyl) -2morpholinopropane-1one
* 4: A-4 2,4-디에틸티오크산톤* 4: A-4 2,4-diethyl thioxanthone
공통 성분:Common Ingredients:
에틸렌성 불포화기 함유 화합물: 디펜타에리트리톨헥사아크릴레이트(닛본 가야꾸사 제조의 DPHA) 20부Ethylenic unsaturated group containing compound: 20 parts of dipentaerythritol hexaacrylate (DPHA by Nippon Kayaku Co., Ltd.)
열경화성 수지: 페놀노볼락형 에폭시 수지 15부Thermosetting resin: 15 parts of phenol novolac type epoxy resin
안료: C.I. 피그먼트 블루 15:3 0.3부 Pigment: C.I. Pigment Blue 15: 3 0.3
C.I. 피그먼트 옐로우 147 0.8부 C.I. Pigment Yellow 147 0.8
열경화 촉매: 멜라민 5부 Thermosetting Catalysts: Melamine Part 5
연쇄 이동제겸 밀착성 부여제: 머캅토벤조티아졸 0.5부Chain transfer agent and adhesion imparting agent: 0.5 parts of mercaptobenzothiazole
틱소트로픽성 부여제: 히드로탈사이트(교와 가가꾸 고교사 제조) 6부Thixotropic imparting agent: 6 parts of hydrotalcite (manufactured by Kyowa Chemical Co., Ltd.)
실리콘계 소포제 3부3 parts of silicone antifoam
유기 용제: DPM(디프로필렌글리콜모노메틸에테르) 5부Organic solvent: 5 parts of DPM (dipropylene glycol monomethyl ether)
충전재: 황산바륨(사카이 가가꾸사 제조의 황산바륨 B30) 100부Filling material: 100 parts of barium sulfate (barium sulfate B30 manufactured by Sakai Chemical Industries, Ltd.)
[성능 평가][Performance evaluation]
<최적 노광량> <Optimum exposure dose>
구리 두께 35 ㎛의 회로 패턴 기판을 버프 롤 연마 후, 수세, 건조하고, 스크린 인쇄법에 의해 실시예 및 비교예의 광경화성 수지 조성물을 전체면에 도포하였다. 이것을 80℃의 열풍 순환식 건조로에서 60분간 건조시켰다.The circuit pattern board | substrate of copper thickness 35 micrometers was rinsed and rinsed after buff roll polishing, and the photocurable resin composition of an Example and a comparative example was apply | coated to the whole surface by the screen printing method. This was dried for 60 minutes in a hot air circulation drying furnace at 80 ° C.
이 기판을 고압 수은등 탑재 노광 장치(수은 쇼트 아크 램프 탑재 노광기 오크 세이사꾸쇼사 제조), 고압 수은등 직묘 노광 장치(초고압 수은등 램프 탑재 직묘 노광기 다이닛본 스크린사 제조의 마큘렉스(Marculex; 등록상표)), 및 직접 묘화 장치(405 nm 레이저 노광 장치 히다치 비어메카닉스사 제조)를 이용하고, 각각 스텝 타블렛(코닥(Kodak) No2)을 통해 노광하였다. 또한, 이 기판을 온도: 30℃, 스프레이압: 0.2 MPa, 현상액: 1 질량% 탄산나트륨 수용액의 조건으로 60초간 현상하고, 잔존하는 스텝타블렛의 패턴이 7단인 때를 최적 노광량으로 하였다.This board is a high pressure mercury lamp mounted exposure apparatus (mercury short arc lamp mounted exposure machine manufactured by Oak Seisakusho Co., Ltd.), a high pressure mercury lamp direct drawing exposure apparatus (super high pressure mercury lamp lamp direct drawing exposure machine manufactured by Dainippon Screen Corporation (Marculex; registered trademark)) And a direct drawing apparatus (405 nm laser exposure apparatus manufactured by Hitachi Beer Mechanics Co., Ltd.), and exposed through a step tablet (Kodak No2), respectively. Moreover, this board | substrate was developed for 60 second on condition of temperature: 30 degreeC, spray pressure: 0.2 MPa, and developing solution: 1 mass% sodium carbonate aqueous solution, and made the optimum exposure amount when the pattern of the remaining step tablet is seven steps.
<최대 현상 수명> <Maximum developing life>
각 실시예 및 비교예의 광경화성 수지 조성물을 패턴 형성된 동박 기판 상에 스크린 인쇄로 전체면 도포하고, 80℃에서 건조하고, 20분부터 80분까지 10분 간격으로 기판을 취출하고, 실온까지 방냉하였다.The photocurable resin composition of each Example and the comparative example was apply | coated whole surface by the screen printing on the patterned copper foil board | substrate, dried at 80 degreeC, the board | substrate was taken out every 10 minutes from 20 minutes to 80 minutes, and it cooled to room temperature. .
이 기판을 온도: 30℃, 스프레이압: 0.2 MPa, 현상액: 1 질량% 탄산나트륨 수용액의 조건으로 60초간 현상하여, 잔사가 남지 않는 최대 허용 건조 시간을 최대 현상 수명으로 하였다.This board | substrate was developed for 60 second on condition of the temperature of 30 degreeC, spray pressure: 0.2 Mpa, and developing solution: 1 mass% sodium carbonate aqueous solution, and the maximum allowable drying time which a residue does not remain was made into the maximum developing life.
[특성 평가][Characteristic evaluation]
각 실시예 및 비교예의 광경화성 수지 조성물을 패턴 형성된 동박 기판 상에 스크린 인쇄로 전체면 도포하고, 실온까지 방냉하였다. 이 기판에 수은 쇼트 아크 램프를 탑재한 노광 장치를 이용하여, 최적 노광량으로 솔더 레지스트 패턴을 노광하였다.The photocurable resin composition of each Example and the comparative example was apply | coated whole surface by screen printing on the patterned copper foil board | substrate, and it cooled to room temperature. The soldering resist pattern was exposed by the optimal exposure amount using the exposure apparatus which mounted the mercury short arc lamp on this board | substrate.
그리고, 이 기판을 온도: 30℃, 스프레이압: 0.2 MPa, 현상액: 1 질량% 탄산나트륨 수용액의 조건으로 60초간 현상하여 레지스트 패턴을 얻었다. 또한, 이 기판을 UV 컨베어로에서 적산 노광량 1000 mJ/㎠의 조건으로 자외선 조사한 후, 150℃에서 60분 가열하여 경화하였다.And this board | substrate was developed for 60 second on condition of the temperature of 30 degreeC, spray pressure: 0.2 Mpa, and developing solution: 1 mass% sodium carbonate aqueous solution, and the resist pattern was obtained. Further, the substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm 2 using a UV conveyor, and then heated at 150 ° C. for 60 minutes to cure.
얻어진 인쇄 기판(평가 기판)에 대하여 이하와 같이 특성을 평가하였다.The properties of the obtained printed board (evaluation board) were evaluated as follows.
<땜납 내열성> ≪ Soldering heat resistance &
로진계 플럭스를 도포한 평가 기판을 미리 260℃로 설정한 땜납조에 침지하고, 변성 알코올로 플럭스를 세정한 후, 육안에 의한 레지스트층의 부풀어오름·박리에 대하여 평가하였다. 판정 기준은 이하와 같다.The evaluation board | substrate with which the rosin type flux was apply | coated was immersed in the solder tank previously set to 260 degreeC, and the flux was wash | cleaned with denatured alcohol, and it evaluated about swelling and peeling of the resist layer by visual observation. The criteria are as follows.
○: 10초간 침지를 3회 이상 반복하더라도 박리가 보이지 않음(Circle): Peeling is not seen even if it repeats immersion 3 times or more for 10 second.
△: 10초간 침지를 3회 이상 반복하면 조금 박리됨(Triangle | delta): It peels a little when repeating immersion 3 times or more for 10 second.
×: 10초간 침지를 3회 이내에 레지스트층에 부풀어오름, 박리가 있음X: swelled in a resist layer within 3 times of immersion for 10 second, and there exists peeling
<무전해 금도금 내성> Electroless Gold Plating Resistant
시판품인 무전해 니켈 도금욕 및 무전해 금도금욕을 이용하여 니켈 0.5 ㎛, 금 0.03 ㎛의 조건으로 도금을 행하여, 도금의 스며듦의 유무를 평가한 후, 테이프 필링에 의해 레지스트층의 박리의 유무를 평가하였다. 판정 기준은 이하와 같다.Plating was performed under conditions of 0.5 μm nickel and 0.03 μm gold using an electroless nickel plating bath and an electroless gold plating bath, which are commercially available products. Evaluated. The criteria are as follows.
◎: 스며듦, 박리가 보이지 않음◎: no seepage and peeling
○: 도금 후에 조금 스며듦이 확인되지만, 테이프 필 후에는 박리되지 않음(Circle): Slightly penetrated after plating, but does not peel off after tape peeling.
△: 도금 후에 아주 약간 스며듦이 보이고, 테이프 필 후에 박리도 보임(Triangle | delta): Very slight seepage after plating, peeling is also seen after tape peeling.
×: 도금 후에 박리가 있음X: peeling after plating
<전기 절연 특성> <Electric Insulation Characteristics>
동박 기판에 IPCB-25의 빗형 전극 B 쿠폰을 이용하였다. 이 빗형 전극에 DC 100V의 바이어스 전압을 인가하고, 85℃, 85% R.H.의 항온항습조에서 1,000시간 후의 마이그레이션의 유무를 확인하였다. 판정 기준은 이하와 같다.The comb-shaped electrode B coupon of IPCB-25 was used for the copper foil substrate. A bias voltage of DC 100V was applied to this comb-shaped electrode, and the presence or absence of the migration after 1,000 hours was confirmed by 85 degreeC and the constant temperature / humidity tank of 85% R.H. The criteria are as follows.
◎: 전혀 변화가 보이지 않는 것◎: no change at all
○: 극히 약간 변화한 것○: extremely slightly changed
△: 변색이 보임 △: discoloration is seen
×: 마이그레이션이 발생하고 있는 것×: The migration is occurring
이들 평가 결과를 표 2에 나타내었다.These evaluation results are shown in Table 2.
[드라이 필름 평가][Dry Film Evaluation]
실시예 1, 2 및 비교예 1, 2의 광경화성 수지 조성물을 메틸에틸케톤으로 희석하고, PET 필름 상에 도포하고, 80℃에서 30분 건조하여, 두께 20 ㎛의 수지 조성물층을 형성하였다. 또한 그 위에 커버 필름을 접합시켜 드라이 필름을 제작하고, 각각을 실시예 9, 10 및 비교예 3, 4로 하였다. 그리고, 커버 필름을 박리하고, 패턴 형성된 동박 기판에 필름을 열라미네이트하여, 동박 기판 상에 수지 조성물층을 밀착시켰다.The photocurable resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were diluted with methyl ethyl ketone, coated on a PET film, and dried at 80 ° C. for 30 minutes to form a resin composition layer having a thickness of 20 μm. Moreover, the cover film was bonded together on it, the dry film was produced, and it was set as Example 9, 10 and Comparative Examples 3 and 4, respectively. And the cover film was peeled off, the film was heat-laminated to the patterned copper foil board | substrate, and the resin composition layer was stuck on the copper foil board | substrate.
이와 같이 하여 얻어진 기판에 대해서, 광경화성 수지 조성물을 도포하여 형성된 기판과 동일하게 노광하였다. 또한, 노광에는 고압 수은등 탑재 노광 장치(수은 쇼트 아크 램프 탑재 노광기 오크 세이사꾸쇼사 제조), 및 직접 묘화 장치(355 nm 레이저 노광 장치 오르보테크사 제조의 파라곤(Paragon) 8000)를 이용하였다.The substrate thus obtained was exposed in the same manner as the substrate formed by applying the photocurable resin composition. In addition, the high pressure mercury lamp mounting exposure apparatus (mercury shot arc lamp mounting exposure machine made by Oak Seisakusho Co., Ltd.), and the direct drawing apparatus (355 nm laser exposure apparatus Orbotech Co., Ltd. product Paragon 8000) were used.
그리고, 캐리어 필름을 박리한 후, 이 기판을 온도: 30℃, 스프레이압: 0.2 MPa, 현상액: 1 질량% 탄산나트륨 수용액의 조건으로 60초간 현상하여 레지스트 패턴을 얻었다. 또한, 150℃의 열풍 건조기로 60분 가열 경화를 행한 후, 마찬가지로 자외선 조사를 행하여 드라이 필름 평가용의 시험 기판을 제작하였다.And after peeling a carrier film, this board | substrate was developed for 60 second on condition of temperature: 30 degreeC, spray pressure: 0.2MPa, developing solution: 1 mass% sodium carbonate aqueous solution, and the resist pattern was obtained. Moreover, after heat-hardening for 60 minutes with the 150 degreeC hot air dryer, ultraviolet irradiation was similarly performed and the test board | substrate for dry film evaluation was produced.
얻어진 시험 기판에 대해서, 마찬가지로, 각 특성의 평가 시험을 행하였다.About the obtained test board | substrate, the evaluation test of each characteristic was similarly performed.
이들 평가 결과를 표 3에 나타내었다.The evaluation results are shown in Table 3.
이와 같이, 본 실시 형태의 광경화성 수지 조성물 및 그의 드라이 필름을 이용함으로써 고감도이고, 단시간의 노광이 가능해짐과 동시에, 현상성을 열화시키지 않고, 양호한 땜납 내열성, 무전해 도금 내성, 전기 절연 특성 등의 신뢰성을 얻을 수 있는 것을 알 수 있다. 그리고, 이러한 광경화성 수지 조성물을 이용함으로써 다이렉트 노광 등의 높은 위치 정렬 정밀도를 갖는 노광 장치를 이용할 때에 있어서도 높은 생산성을 얻는 것이 가능해진다.Thus, by using the photocurable resin composition of this embodiment and its dry film, it is highly sensitive and short-time exposure is possible, and it does not deteriorate developability, and it is favorable solder heat resistance, electroless plating resistance, electrical insulation characteristics, etc. It can be seen that the reliability of can be obtained. And by using such a photocurable resin composition, even when using the exposure apparatus which has high alignment accuracy, such as direct exposure, it becomes possible to obtain high productivity.
[아웃 가스량 평가] [Out gas amount evaluation]
수지 용액 B-1을 이용하여, 표 4에 나타내는 배합(질량부)으로 배합하고, 동일하게 하여 실시예 11, 12, 비교예 5, 6의 솔더 레지스트용 광경화성 수지 조성물을 제조하였다. 또한, A-1은 실시예 1 내지 8에서 이용된 광중합 개시제이다.Using resin solution B-1, it mix | blended by the compounding (mass part) shown in Table 4, and carried out similarly to manufacture the photocurable resin composition for soldering resists of Examples 11 and 12 and Comparative Examples 5 and 6. In addition, A-1 is a photoinitiator used in Examples 1-8.
* 5: A-5* 5: A-5
* 6: A-6* 6: A-6
1,2-옥탄디온-1-[4-(페닐티오)페닐]-2-(O-벤조일옥심)(바스프 재팬사 제조의 IRG-OXE01)1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (IRG-OXE01 by BASF Japan)
* 7: A-7(바스프 재팬사 제조의 Irg907)* 7: A-7 (IRG907 by BASF Japan company)
* 8: 트리메틸올프로판트리아크릴레이트* 8: trimethylolpropanetriacrylate
* 9: 비스페놀 A 디글리시딜에테르(미쯔비시 가가꾸사 제조)* 9: Bisphenol A diglycidyl ether (made by Mitsubishi Chemical Corporation)
* 10: 중합 금지제 페노티아진* 10: polymerization inhibitor phenothiazine
이들 광경화성 수지 조성물을 유리 기판 상에 스크린 인쇄에 의해 도포하고, 열풍 순환식 건조로를 이용하여 80℃에서 30분간 건조한 후, 오크 세이사꾸쇼사 제조 고압 수은등 노광 장치를 이용하여 적정 노광량으로 노광하였다.After apply | coating these photocurable resin compositions on a glass substrate by screen printing, and drying at 80 degreeC for 30 minute (s) using a hot air circulation type drying furnace, it exposed at the appropriate exposure amount using the high pressure mercury lamp exposure apparatus by Oak Seisakusho Co., Ltd. .
그리고, 그의 일부에 대해서 그대로 도막을 깎아내어 열경화 전 샘플로 하고, 나머지를 150℃에서 60분간 경화한 후, 도막을 깎아내어 열경화 후 샘플로 하였다.And a part of the coating film was scraped off as it is, and it was set as the sample before thermosetting, and the remainder was hardened at 150 degreeC for 60 minutes, and the coating film was scraped off and it was set as the sample after thermosetting.
각각의 샘플 1 mg을, 퍼징&트랩으로 열경화 전 샘플은 150℃에서 5분간 및 150℃에서 30분간, 열경화 후 샘플은 245℃에서 5분간 가열하고, 발생한 광중합 개시제 성분을 가스 크로마토그래프로 정량하였다.1 mg of each sample was heated by purging & trapping for 5 minutes at 150 ° C for 5 minutes and at 150 ° C for 30 minutes, after thermosetting for 5 minutes at 245 ° C. Quantification
이 때의 적정 노광량과, 발생한 광중합 개시제 유래의 휘발 성분(아웃 가스)의 정량 결과를 표 5에 나타내었다.Table 5 shows the appropriate exposure dose and the quantitative results of the volatile components (out gas) derived from the generated photopolymerization initiator.
* 11 0.1% 미만11 less than 0.1%
이와 같이, 본 실시 형태의 광경화성 수지 조성물에 있어서는, 높은 감도를 가짐과 동시에, 열경화 전 샘플, 열경화 후 샘플 중 어느 것에 있어서도 광중합 개시제 유래의 휘발 성분(아웃 가스)량을 억제할 수 있는 것을 알 수 있다. 따라서, 다이렉트 노광 등에 의한 노광 시, 또는 후속 공정에서의 리플로우에 의한 실장 시 등에 있어서의 오염을 억제하는 것이 가능해진다.Thus, in the photocurable resin composition of this embodiment, while having high sensitivity, the amount of volatile components (out gas) derived from a photoinitiator can be suppressed also in the sample before thermosetting and the sample after thermosetting. It can be seen that. Therefore, it becomes possible to suppress contamination at the time of exposure by direct exposure etc. or at the time of mounting by reflow in a subsequent process.
Claims (7)
카르복실기 함유 수지,
분자 중에 2개 이상의 에틸렌성 불포화기를 갖는 화합물, 및
열경화성 수지를 포함하는 것을 특징으로 하는 광경화성 수지 조성물.
<화학식 I>
(식 중, R1은 수소 원자, 탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 페닐기, 페닐기(탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 아미노기, 탄소수 1 내지 8의 알킬기를 갖는 알킬아미노기 또는 디알킬아미노기에 의해 치환되어 있음), 나프틸기(탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 아미노기, 탄소수 1 내지 8의 알킬기를 갖는 알킬아미노기 또는 디알킬아미노기에 의해 치환되어 있음)를 나타내고, R2, R3은 각각 수소 원자, 탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 할로겐기, 페닐기, 페닐기(탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 아미노기, 탄소수 1 내지 8의 알킬기를 갖는 알킬아미노기 또는 디알킬아미노기에 의해 치환되어 있음), 나프틸기(탄소수 1 내지 17의 알킬기, 탄소수 1 내지 8의 알콕시기, 아미노기, 탄소수 1 내지 8의 알킬기를 갖는 알킬아미노기 또는 디알킬아미노기에 의해 치환되어 있음), 안트릴기, 피리딜기, 벤조푸릴기, 벤조티에닐기를 나타내고, Ar은 결합이나, 탄소수 1 내지 10의 알킬렌, 비닐렌, 페닐렌, 비페닐렌, 피리딜렌, 나프틸렌, 안트릴렌, 티에닐렌, 푸릴렌, 2,5-피롤-디일, 4,4'-스틸벤-디일, 4,2'-스티렌-디일을 나타내고, n은 0 내지 1의 정수를 나타냄)A photopolymerization initiator having two oxime ester groups in a molecule represented by the following formula (I),
Carboxyl group-containing resin,
A compound having two or more ethylenically unsaturated groups in a molecule, and
A thermosetting resin is included, The photocurable resin composition characterized by the above-mentioned.
(I)
(In formula, R <1> is a hydrogen atom, a C1-C17 alkyl group, a C1-C8 alkoxy group, a phenyl group, a phenyl group (C1-C17 alkyl group, a C1-C8 alkoxy group, an amino group, C1-C8). Substituted by an alkylamino or dialkylamino group having an alkyl group of 1), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkyl group) Substituted with an amino group), and R 2 and R 3 each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, and a phenyl group (alkyl group having 1 to 17 carbon atoms and carbon atoms). Substituted by an alkylamino group or dialkylamino group having 1 to 8 alkoxy groups, amino groups, alkyl groups having 1 to 8 carbon atoms, and naphthyl groups (alkyl groups having 1 to 17 carbon atoms, 1 carbon atom). And an alkoxy group, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar represents a bond. Alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, anthylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene -Diyl, 4,2'-styrene-diyl, n represents an integer from 0 to 1)
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TWI476526B (en) | 2015-03-11 |
US20120111620A1 (en) | 2012-05-10 |
JP5236587B2 (en) | 2013-07-17 |
CN102472968A (en) | 2012-05-23 |
TW201128308A (en) | 2011-08-16 |
US8748502B2 (en) | 2014-06-10 |
JP2011022328A (en) | 2011-02-03 |
WO2011007566A1 (en) | 2011-01-20 |
CN102472968B (en) | 2014-04-23 |
KR20120026619A (en) | 2012-03-19 |
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